CN101891708A - Diacylhydrazine compounds containing 4-methyl-1,2,3-thiadiazole groups, preparation method and application thereof - Google Patents
Diacylhydrazine compounds containing 4-methyl-1,2,3-thiadiazole groups, preparation method and application thereof Download PDFInfo
- Publication number
- CN101891708A CN101891708A CN 201010187048 CN201010187048A CN101891708A CN 101891708 A CN101891708 A CN 101891708A CN 201010187048 CN201010187048 CN 201010187048 CN 201010187048 A CN201010187048 A CN 201010187048A CN 101891708 A CN101891708 A CN 101891708A
- Authority
- CN
- China
- Prior art keywords
- thiadiazoles
- milliliters
- methyl isophthalic
- isophthalic acid
- tertiary butyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention provides diacylhydrazine derivatives containing 1,2,3-thiadiazole groups, a preparation method and application thereof, and relates to heterocyclic compounds containing 1,2,3-thiadiazole, which have chemical structural general formulas shown in a graph I, a graph II, a graph III, a graph IV, a graph V and a graph VI. The invention discloses the structural general formulas, a synthesizing method, application in pesticide, fungicide, antiphytovirucide and plant activator of the compounds, and a process for preparing the pesticide, the fungicide, the antiphytovirucide and the plant activator by mixing the compounds and agriculturally accepted auxiliaries or synergist, and further discloses application and a preparation method for combining the compounds with commodity pesticide, the fungicide, the antiphytovirucide and the plant activator in controlling diseases, insect pests, virus diseases of agriculture, forestry and gardening.
Description
Technical field
Technical scheme of the present invention relates to and contains 1; the heterogeneous ring compound of 2-diazole; be specifically related to contain the 4-methyl isophthalic acid; 2; the bishydrazide derivative of 3-thiadiazoles group; more specifically relate to N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-the N '-tertiary butyl-N '-substituted formyl hydrazine class compound; N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-the N-tertiary butyl-N '-substituted formyl hydrazine class compound; N '-the tertiary butyl-N '-substituted formacyl-N-substituted formacyl-N-4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl hydrazine compounds; N '-the tertiary butyl-N-substituted formacyl-N-4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl hydrazine compounds; N '-the tertiary butyl-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N-substituted formacyl-N-4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl hydrazine compounds and two-[(N '-tertiary butyl-N '-substituted formacyl)-N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl hydrazine)] compounds.
Background technology
Bishydrazide compounds obtained at aspects such as agricultural chemicals, bio-medical material, electroluminescent, selectivity identification and liquid crystal materials widespread use (Gao Wei, etc. chemical industry progress, 2009,28 (5): 882-889).At pesticide field, triazolo pyrimidine thioether bishydrazide compounds have the activity that suppresses the test plant growth (Xia Bo, etc. Chinese agricultural chemicals, 2007,6:48-51); Tertiary butyl bishydrazide compound is a big class insect growth regulator(IGR), and this class medicament is a target of attack with the distinctive system of growing of insect, utilizes the hormone substance that different steps produced in the insect growth process, grows normally with interference insect.U.S. Rohm-Hass company reported first in 1988 the N-tertiary butyl bishydrazide compounds RH-5849 of synthetic have corresponding plan moulting hormone effect (Wing.Science.1988,241:467), and successfully it is developed as commercial pesticide species press down the food hydrazine (Feng Jian. modern agricultural chemicals, 2004,3 (2): 4-8).Subsequently, the said firm is guide's active structure with RH-5849 again, utilize in the pesticide molecule design etc. row's principle and roughly the same the synthetic method it has been carried out structural modification, successfully developed RH-5992 (Heller again, et al., Brighton Crop.Prot.Conf., Pests﹠amp; Dis., 1992,1:59), RH-2485 (Le, et al., Brighton Crop.Prot.Conf., Pests﹠amp; Dis., 1996,2:481), RH-0345 (Cowles, et al., J.Econ.Entomol., 1996,89:1556) three kinds of commercialization kinds.The nineties in 20th century, the Japan scientist has reported the progress of bishydrazide compounds successively, with N-tertiary butyl bishydrazide or be first guide structure only with two acylhydrazines, conversion two ends acyl group contains phenyl ring, heterocycle, the fused heterocycle with different substituents, Nippon Kayaku Co.Ltd and Sankyo Co.Ltd have developed jointly two aromatic hydrazide kind compound ANS-118 (the Yanagi et al. that contains benzheterocycle, BrightonCrop.Prot.Conf., Pests﹠amp; Dis., 2000,2:27).N-tertiary butyl bishydrazide compounds becomes the commercial insect growth regulator(IGR) of another class after neotonin and chitin synthesis inhibitor, is widely used in the control of insect.China's Jiangsu pesticide research cumarone introduced in the structure of bishydrazide developed furans worm hydrazides, this compound shows very high insecticidal activity to lepidoptera pest armyworm and beet armyworm, obtain China's novel pesticide and registered (Zhang Xiangning temporarily, Deng. Agricultural University Of Nanjing's journal, 2005,28 (4): 135-139).
The general structure of bishydrazide sterilant
China is very active in the initiative research in this field, small ring compound is introduced in the bishydrazide molecule synthetic cyclopropane bishydrazide compound as 1,1 '-ethyl dicarboxylate's gem-dimethyl cyclopropane bishydrazide has better insecticidal activity (Su Jiangtao to the broad bean aphid, Deng. agricultural chemicals, 2006,45 (11): 737-738); The N-tertiary butyl-N-substituted benzoyl hydrazides (or contain on the phenyl ring amino bishydrazide compound) have good larvicidal activity (the hair light of spring, etc. organic chemistry, 2006,26 (1): 60-64); That the derivative of heterocycle bishydrazide compound such as chroman also has is synthetic (Huang Zhiqiang, etc. organic chemistry, 2009,29 (6): 891-897); Fused heterocycle and contain the activity that the ferrocene substituted aryl also can improve compound, contain the bishydrazide compounds of trifluoro ethoxy on the phenyl ring and do not contain the N-tertiary butyl and also show in various degree biological activity (Cui Zining, Deng. organic chemistry, 2007,27 (10): 1300-1304).Relatively more outstanding is, the yellow profit autumn of Nankai University and the people of Wangqing County teach seminar and will find that new compound shows mosquito larvae and the good biological activity of small cabbage moth (Sun Ranfeng in N-S-N or the N-S-S-N key introducing bishydrazide structure, et al.J.Agric.FoodChem., 2009,57 (9): 3661-3668), part of compounds has good DEVELOPMENT PROSPECT.
Many bibliographical informations the composition optimizes and the biological activity of aryl class bishydrazide lead compound, but with 1,2,3-thiadiazoles active structure fragment introduces that structure in the bishydrazide molecule is derived and biological activity report very few (200910069470.2).Because 1,2, the 3-thiadiazoles heterocyclic compounds has wide biological activity, as (Boschelli, et al., J.Med.Chem.1993,36:1802 such as anti-inflammatory, expelling parasite, weeding, coordinate plant growth; Saad H., Indian J.Chem, 1996,35B:980; Bakulev, et al., The Chemistry of 1,2,3-thiadiazole, 2004, John Wiley ﹠amp; Sons, Inc.), the first thiophene lures amine (Fan Zhijin etc., CN1810808A; Fan Zhijin etc., CN2020667A), diazosulfide (BTH) and tiadinil (TDL) all be 1,2, the derivative of 3-thiadiazoles (Ni Changchun, world's agricultural chemicals, 2007,29 (1): 18-23).Based on above-mentioned document analysis and patent investigation, novelty of the present invention be lead compound with existing two aromatic hydrazide kind insect growth regulator(IGR)s, according to structure activity relationship and bioisostere, the principle and the means of the design of agricultural chemicals such as active substructure splicing, existing two aromatic hydrazide kind insect growth regulator(IGR)s are carried out further composition optimizes, the a series of 4-of containing methyl isophthalic acids have been synthesized in design, 2, the bishydrazide compounds of 3-thiadiazoles-N-tertiary butyl, and the synthetic new compound has been carried out the evaluated biological activity of system, the biological activity of these compounds all has raising comparatively significantly than the positive control compound, and the present invention is efficient, synthetic and the exploitation of low toxicity and eco-friendly novel pesticide molecular designing provides the candidate compound.
Summary of the invention
Technical problem to be solved by this invention is: the new 4-methyl isophthalic acid that contains is provided, 2, the synthetic method of the bishydrazide derivative of 3-thiadiazoles group, provide this compounds to suppress agricultural, gardening and forestry pathogenic fungi, biological activity of insect and plant virus and the growth of regulating insect, inducing plant produces the purposes of anti-disease activity and the working method of these medicaments, provide simultaneously the use of these compounds and commercially available agricultural chemical breed combination in agriculture field and gardening field and field of forestry application and with agricultural on acceptable auxiliary agent or synergistic agent combined preparation sterilant, the complete processing and the working method of desinsection and sterilant and desinsection and Antiphytoviral medicament and desinsection and plant activator composition.
The present invention solves this technical problem the technical scheme that is adopted: what have that agriculture field, gardening field, field of forestry insecticidal activity, fungicidal activity, anti-phytoviral activity and inducing plant produce anti-disease activity or insect growth regulator activity contains the 4-methyl isophthalic acid, 2, the chemical structure of general formula of the bishydrazide derivative of 3-thiadiazoles group is suc as formula shown in I, formula II, formula III, formula IV, formula V and the formula VI:
Wherein, R
1, R
2, R
3, R
4, R
5Be respectively and be selected from phenyl, the 2-aminomethyl phenyl, the 3-aminomethyl phenyl, the 4-aminomethyl phenyl, the 2-p-methoxy-phenyl, the 3-p-methoxy-phenyl, the 4-p-methoxy-phenyl, the 2-chloro-phenyl-, the 3-chloro-phenyl-, the 4-chloro-phenyl-, the 2-fluorophenyl, the 3-fluorophenyl, the 4-fluorophenyl, the 2-trifluoromethyl, the 3-trifluoromethyl, the 4-trifluoromethyl, the 2-nitrophenyl, the 3-nitrophenyl, the 4-nitrophenyl, the 4-ethylphenyl, the 4-methyl isophthalic acid, 2, the 3-thiadiazolyl group, the 2-furyl, 2-methyl-2-(4-chloro-phenyl-)-1-propyl group, trichloromethyl, the chrysanthemum acyl group, dichloro chrysanthemum acyl group, 4-fluorobenzene ethyl, 2, the 6-dichlorophenyl, methyl, propyl group, heptyl, 3, the 5-dichlorophenyl, 3, the 5-dimethyl, 3-(2-chloro-phenyl-)-5-methyl-isoxazole-4-base, 2,4-dimethyl-1-phenylpyrazole-3-base, cyclohexyl, 2-fluorobenzene ethyl, 3,6-dichloropyridine-2-base, 5-ethyl-1-methylpyrazole-3-base, the group of 2-fluorobenzene ethyl; Q is arylidene or inferior fatty group.
The 4-methyl isophthalic acid that contains of the present invention, 2, the synthetic method of the bishydrazide derivative I of 3-thiadiazoles group is as follows:
Wherein: R
1For being selected from phenyl; the 2-aminomethyl phenyl; the 3-aminomethyl phenyl; the 4-aminomethyl phenyl; the 2-p-methoxy-phenyl; the 3-p-methoxy-phenyl; the 4-p-methoxy-phenyl; the 2-chloro-phenyl-; the 3-chloro-phenyl-; the 4-chloro-phenyl-; the 2-fluorophenyl; the 3-fluorophenyl; the 4-fluorophenyl; the 2-trifluoromethyl; the 3-trifluoromethyl; the 4-trifluoromethyl; the 2-nitrophenyl; the 3-nitrophenyl; the 4-nitrophenyl; the 4-ethylphenyl; the 4-methyl isophthalic acid; 2; the 3-thiadiazolyl group; the 2-furyl; 2-methyl-2-(4-chloro-phenyl-)-1-propyl group; trichloromethyl; the chrysanthemum acyl group; dichloro chrysanthemum acyl group; 4-fluorobenzene ethyl; 2; the 6-dichlorophenyl; methyl; propyl group; heptyl; 3; the 5-dichlorophenyl; 3; the 5-dimethyl; 3-(2-chloro-phenyl-)-5-methyl-isoxazole-4-base; 2; 4-dimethyl-1-phenylpyrazole-3-base; cyclohexyl; 2-fluorobenzene ethyl; 3,6-dichloropyridine-2-base; 5-ethyl-1-methylpyrazole-3-base; the group of 2-fluorobenzene ethyl.
The 4-methyl isophthalic acid that contains of the present invention, 2, the synthetic method of the bishydrazide derivative I I of 3-thiadiazoles group is as follows:
Wherein: R
2For being selected from phenyl; the 2-aminomethyl phenyl; the 3-aminomethyl phenyl; the 4-aminomethyl phenyl; the 2-p-methoxy-phenyl; the 3-p-methoxy-phenyl; the 4-p-methoxy-phenyl; the 2-chloro-phenyl-; the 3-chloro-phenyl-; the 4-chloro-phenyl-; the 2-fluorophenyl; the 3-fluorophenyl; the 4-fluorophenyl; the 2-trifluoromethyl; the 3-trifluoromethyl; the 4-trifluoromethyl; the 2-nitrophenyl; the 3-nitrophenyl; the 4-nitrophenyl; the 4-ethylphenyl; the 4-methyl isophthalic acid; 2; the 3-thiadiazolyl group; the 2-furyl; 2-methyl-2-(4-chloro-phenyl-)-1-propyl group; trichloromethyl; the chrysanthemum acyl group; dichloro chrysanthemum acyl group; 4-fluorobenzene ethyl; 2; the 6-dichlorophenyl; methyl; propyl group; heptyl; 3; the 5-dichlorophenyl; 3; the 5-dimethyl; 3-(2-chloro-phenyl-)-5-methyl-isoxazole-4-base; 2; 4-dimethyl-1-phenylpyrazole-3-base; cyclohexyl; 2-fluorobenzene ethyl; 3,6-dichloropyridine-2-base; 5-ethyl-1-methylpyrazole-3-base; the group of 2-fluorobenzene ethyl.
The 4-methyl isophthalic acid that contains of the present invention, 2, the synthetic method of the bishydrazide derivative III of 3-thiadiazoles group is as follows:
Wherein: R
3For being selected from phenyl; the 2-aminomethyl phenyl; the 3-aminomethyl phenyl; the 4-aminomethyl phenyl; the 2-p-methoxy-phenyl; the 3-p-methoxy-phenyl; the 4-p-methoxy-phenyl; the 2-chloro-phenyl-; the 3-chloro-phenyl-; the 4-chloro-phenyl-; the 2-fluorophenyl; the 3-fluorophenyl; the 4-fluorophenyl; the 2-trifluoromethyl; the 3-trifluoromethyl; the 4-trifluoromethyl; the 2-nitrophenyl; the 3-nitrophenyl; the 4-nitrophenyl; the 4-ethylphenyl; the 4-methyl isophthalic acid; 2; the 3-thiadiazolyl group; the 2-furyl; 2-methyl-2-(4-chloro-phenyl-)-1-propyl group; trichloromethyl; the chrysanthemum acyl group; dichloro chrysanthemum acyl group; 4-fluorobenzene ethyl; 2; the 6-dichlorophenyl; methyl; propyl group; heptyl; 3; the 5-dichlorophenyl; 3; the 5-dimethyl; 3-(2-chloro-phenyl-)-5-methyl-isoxazole-4-base; 2; 4-dimethyl-1-phenylpyrazole-3-base; cyclohexyl; 2-fluorobenzene ethyl; 3,6-dichloropyridine-2-base; 5-ethyl-1-methylpyrazole-3-base; the group of 2-fluorobenzene ethyl.
The 4-methyl isophthalic acid that contains of the present invention, 2, the synthetic method of the bishydrazide derivative I V of 3-thiadiazoles group is as follows:
Wherein: R
4For being selected from phenyl; the 2-aminomethyl phenyl; the 3-aminomethyl phenyl; the 4-aminomethyl phenyl; the 2-p-methoxy-phenyl; the 3-p-methoxy-phenyl; the 4-p-methoxy-phenyl; the 2-chloro-phenyl-; the 3-chloro-phenyl-; the 4-chloro-phenyl-; the 2-fluorophenyl; the 3-fluorophenyl; the 4-fluorophenyl; the 2-trifluoromethyl; the 3-trifluoromethyl; the 4-trifluoromethyl; the 2-nitrophenyl; the 3-nitrophenyl; the 4-nitrophenyl; the 4-ethylphenyl; the 4-methyl isophthalic acid; 2; the 3-thiadiazolyl group; the 2-furyl; 2-methyl-2-(4-chloro-phenyl-)-1-propyl group; trichloromethyl; the chrysanthemum acyl group; dichloro chrysanthemum acyl group; 4-fluorobenzene ethyl; 2; the 6-dichlorophenyl; methyl; propyl group; heptyl; 3; the 5-dichlorophenyl; 3; the 5-dimethyl; 3-(2-chloro-phenyl-)-5-methyl-isoxazole-4-base; 2; 4-dimethyl-1-phenylpyrazole-3-base; cyclohexyl; 2-fluorobenzene ethyl; 3,6-dichloropyridine-2-base; 5-ethyl-1-methylpyrazole-3-base; the group of 2-fluorobenzene ethyl.
The 4-methyl isophthalic acid that contains of the present invention, 2, the synthetic method of the bishydrazide derivative V of 3-thiadiazoles group is as follows:
Wherein: R
5For being selected from phenyl; the 2-aminomethyl phenyl; the 3-aminomethyl phenyl; the 4-aminomethyl phenyl; the 2-p-methoxy-phenyl; the 3-p-methoxy-phenyl; the 4-p-methoxy-phenyl; the 2-chloro-phenyl-; the 3-chloro-phenyl-; the 4-chloro-phenyl-; the 2-fluorophenyl; the 3-fluorophenyl; the 4-fluorophenyl; the 2-trifluoromethyl; the 3-trifluoromethyl; the 4-trifluoromethyl; the 2-nitrophenyl; the 3-nitrophenyl; the 4-nitrophenyl; the 4-ethylphenyl; the 4-methyl isophthalic acid; 2; the 3-thiadiazolyl group; the 2-furyl; 2-methyl-2-(4-chloro-phenyl-)-1-propyl group; trichloromethyl; the chrysanthemum acyl group; dichloro chrysanthemum acyl group; 4-fluorobenzene ethyl; 2; the 6-dichlorophenyl; methyl; propyl group; heptyl; 3; the 5-dichlorophenyl; 3; the 5-dimethyl; 3-(2-chloro-phenyl-)-5-methyl-isoxazole-4-base; 2; 4-dimethyl-1-phenylpyrazole-3-base; cyclohexyl; 2-fluorobenzene ethyl; 3,6-dichloropyridine-2-base; 5-ethyl-1-methylpyrazole-3-base; the group of 2-fluorobenzene ethyl.
Of the present inventionly contain 1,2, the synthetic method of the bishydrazide derivative VI of 3-thiadiazoles active group is as follows:
Wherein: Q is arylidene or inferior fatty group, as
Deng.
Specifically be divided into following steps:
A. the preparation of substituted formyl chlorine:
The replacement formic acid that adds 2 mmoles in 50 milliliters of round-bottomed flasks adds the sulfur oxychloride of 12 mmoles again, with reaction mixture with oil bath reflux 3-4 hour, air distillation remove behind the intact sulfur oxychloride of unreacted substituted formyl chlorine, sealing is preserved standby; The amount of substituted formyl chlorine preparation enlarges by corresponding proportion or dwindles.
The preparation of B.N-(substituted formacyl)-N '-tertiary butyl hydrazine:
In 100 milliliters of round-bottomed flasks, add 15 mmole tertiary butyl hydrazonium salt hydrochlorates, add 40 milliliters of methylene dichloride and 5 ml waters and 30 mmole sodium hydroxide again, under induction stirring and ice bath cooling, slowly drip 20 milliliters of dichloromethane solutions of 15 mmole substituted formyl chlorine, dropwise the back room temperature reaction 3 hours, the stopped reaction afterreaction mixes nothing and washes with water, tell organic layer, behind the anhydrous magnesium sulfate drying, removal of solvent under reduced pressure obtains N-(substituted formacyl)-N '-tertiary butyl hydrazine, and product need not to be further purified the reaction that is directly used in next step; The amount of N-(substituted formacyl)-N '-tertiary butyl hydrazine preparation enlarges by corresponding proportion or dwindles.
C.4-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-5-formyl chloride:
4-methyl isophthalic acid with 9.66 gram (0.067 mole) synthetic or purchase, 2,3-thiadiazoles-5-formic acid and 29 milliliters of thionyl chlorides join in 100 milliliters of three mouthfuls of round-bottomed flasks, 80 degrees centigrade of following reflux 6 hours, remove excessive thionyl chloride under reduced pressure, underpressure distillation is collected 94-96 degree centigrade cut and is got faint yellow product 9.25 grams under 2000Pa, column chromatography purification, productive rate: 85%, intermediate 4-methyl isophthalic acid, 2, the 3-thiadiazoles-sealing of 5-formyl chloride is kept in the moisture eliminator standby, the 4-methyl isophthalic acid, 2, the amount of 3-thiadiazoles-5-formyl chloride preparation enlarges by corresponding proportion or dwindles.
The preparation of D.N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine:
In 1000 milliliters of round-bottomed flasks, add 0.4 mole of tertiary butyl hydrazonium salt hydrochlorate, add 450 milliliters of methylene dichloride and 100 ml waters and 0.6 molar sodium hydroxide again, under induction stirring and ice bath cooling, slowly drip 0.4 mole of 4-methyl isophthalic acid, 2,50 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, dropwise the back room temperature reaction 5 hours, the stopped reaction afterreaction mixes nothing and washes with water, tell organic layer, behind the anhydrous magnesium sulfate drying, removal of solvent under reduced pressure obtains N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-and N '-tertiary butyl hydrazine, product need not to be further purified the reaction that is directly used in next step; The amount of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine preparation enlarges by corresponding proportion or dwindles.
The preparation of E.N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-the formyl radical)-N '-tertiary butyl-N '-substituted formyl hydrazine class compound I:
Get 0.1 mmole N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, join in 50 milliliters of round-bottomed flasks, add acid binding agent 0.12 mmole triethylamine then, the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.1 mmole substituted formyl chlorine down; Dropwise the back and continued stirring reaction 4 hours in room temperature; after reaction finishes; the reaction mixture water is given a baby a bath on the third day after its birth inferior; anhydrous magnesium sulfate drying filters the back removal of solvent under reduced pressure, and crude product is with Virahol or re-crystallizing in ethyl acetate; obtain N-(4-methyl isophthalic acid; 2,3-thiadiazoles-5-formyl radical)-the N '-tertiary butyl-N '-substituted formyl hydrazine class compound I, carry out fusing point and
1The mensuration of H NMR is determined its chemical structure, and the amount of Compound I preparation enlarges by corresponding proportion or dwindles; The chemical structure of Compound I sees Table 1.
The preparation of F.N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-the formyl radical)-N-tertiary butyl-N '-substituted formyl hydrazine class compound II:
Getting 0.1 mmole N-(substituted formacyl)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, join then in 50 milliliters of round-bottomed flasks, add acid binding agent 0.12 mmole triethylamine, the ice bath cooling slowly drips 0.1 mmole 4-methyl isophthalic acid down, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride; Dropwise the back and continued stirring reaction 4 hours in room temperature; after reaction finishes; the reaction mixture water is given a baby a bath on the third day after its birth inferior; anhydrous magnesium sulfate drying spends the night, and filters the back removal of solvent under reduced pressure, and crude product is with Virahol or re-crystallizing in ethyl acetate; obtain N-(4-methyl isophthalic acid; 2,3-thiadiazoles-5-formyl radical)-the N-tertiary butyl-N '-substituted formyl hydrazine class compound II, carry out fusing point and
1The mensuration of H NMR is determined its chemical structure, and the amount of Compound I I preparation enlarges by corresponding proportion or dwindles; The chemical structure of Compound I I sees Table 1.
G.N '-the tertiary butyl-N '-substituted formacyl-N-substituted formacyl-N-4-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-5-formyl hydrazine derivative III
In 100 milliliters of round-bottomed flasks, add 0.1 mmole N '-tertiary butyl-4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl hydrazine, 0.2 the triethylamine of mmole, 20 milliliters of methylene dichloride stirring and dissolving slowly drip 10 milliliters of dichloromethane solutions that are dissolved with 0.1 mmole substituted formyl chlorine then under condition of ice bath, dropwised in 1 hour, naturally heat up stirring at room 5 hours, saturated NaHCO
3Solution extraction, anhydrous Na
2SO
4Dry; filter; the decompression precipitation; (eluent is 60-90 degree centigrade a sherwood oil: ethyl acetate volume ratio 3: 1) get the product N '-tertiary butyl-N '-substituted formacyl-N-substituted formacyl-N-4-methyl isophthalic acid with 200-300 order silica gel column chromatography; 2; 3-thiadiazoles-5-formyl hydrazine derivative III, carry out fusing point and
1The mensuration of H NMR is determined its chemical structure, and the amount of compound III preparation enlarges by corresponding proportion or dwindles; The chemical structure of compound III sees Table 1.
H.N '-the tertiary butyl-N-substituted formacyl-N-4-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-5-formyl hydrazine derivative I V
Adding 0.1 mmole N-(substituted formacyl)-N '-tertiary butyl hydrazine in 100 milliliters of round-bottomed flasks is dissolved in 20 milliliters of methylene dichloride; add acid binding agent 0.12 mmole triethylamine then; the ice bath cooling slowly drips 0.1 mmole 4-methyl isophthalic acid down; 2; 20 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride; dropwised in 1 hour; naturally heat up; continued stirring reaction 4 hours in room temperature; after reaction finishes; filter the back removal of solvent under reduced pressure; (eluent is 60-90 degree centigrade a sherwood oil to crude product: ethyl acetate volume ratio 3: 1) get N '-tertiary butyl N-substituted formacyl-N-4-methyl isophthalic acid with 200-300 order silica gel column chromatography; 2,3-thiadiazoles-5-formyl hydrazine derivative I V, carry out fusing point and
1The mensuration of HNMR is determined its chemical structure, and the amount of compound IV preparation enlarges by corresponding proportion or dwindles; The chemical structure of compound IV sees Table 1.
I.N '-the tertiary butyl-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N-substituted formacyl-N-4-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-5-formyl hydrazine derivative V
Adding 4.54 mmole N-(substituted formacyl)-N '-tertiary butyl hydrazines in 100 milliliters of round-bottomed flasks is dissolved in 20 milliliters of methylene dichloride; add acid binding agent 6.8 mmole triethylamines then; the ice bath cooling slowly drips 6.8 mmole 4-methyl isophthalic acids down; 2; 20 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride; dropwised in 1 hour; naturally heat up; continued stirring reaction 4 hours in room temperature; after reaction finishes; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous sodium sulfate drying 60-90 degree centigrade sherwood oil: methylene dichloride mixed solvent recrystallization gets N '-tertiary butyl N '-(4-methyl isophthalic acid, 2; 3-thiadiazoles-5-formyl radical)-N-substituted formacyl-N-4-methyl isophthalic acid; 2,3-thiadiazoles-5-formyl hydrazine derivative V, carry out fusing point and
1The mensuration of HNMR is determined its chemical structure, and the amount of compound V preparation enlarges by corresponding proportion or dwindles; The chemical structure of compound IV sees Table 1.
J. the preparation of two-[(N '-tertiary butyl-N '-substituted formacyl)-N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl hydrazine)] derivative VI
In 100 milliliters of round-bottomed flasks, add 7 mmole N '-tertiary butyl-4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl hydrazine; the triethylamine of 8 mmoles; 20 milliliters of methylene dichloride stirring and dissolving; under condition of ice bath, slowly drip then and be dissolved with 3.5 mmoles, dropwise, naturally intensification 5 milliliters of the dichloromethane solutions of substituted dimethyl acyl chlorides; stirring at room 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying, removal of solvent under reduced pressure behind the suction filtration; that sherwood oil and methylene dichloride recrystallization get product is two-[(N '-tertiary butyl-N '-substituted formacyl) N-(4-methyl isophthalic acid; 2,3-thiadiazoles-5-formyl hydrazine)] derivative VI, measure fusing point and
1HNMR determines chemical structure, and the amount of compound VI preparation enlarges by corresponding proportion or dwindles; The chemical structure of compound IV sees Table 1.
K. the 4-methyl isophthalic acid that contains of the present invention, 2, the bishydrazide derivative of 3-thiadiazoles group is to the mensuration of small cabbage moth insecticidal activity:
The 4-methyl isophthalic acid that contains of the present invention, 2, the bishydrazide derivative of 3-thiadiazoles group is as follows to the screening method of the insecticidal activity of small cabbage moth: adopt the blade medicine embrane method; The solution that sample to be tested is mixed with 200 mcg/ml carries out, get former medicine sample earlier with the small amount of acetone dissolving, with the dilution of the 0.5 ‰ Triton-100 aqueous solution, the 0.5 ‰ Triton-100 aqueous solution are contrast then, each concentration repeats for 3 times, 10 examinations of each re-treatment worm; Get fresh free of contamination cabbage leaves, in soup, soaked for 10 seconds, after indoor drying (about 2 hours), put into the culture dish of 9 centimetres of diameters, insert small cabbage moth 2 instar larvaes of big or small basically identical respectively, tighten with bungee and be placed in the small cabbage moth constant temperature insectary check result after 96 hours or 120 hours, touch polypide with little writing brush or tweezers, can not coordinated movement as death; With the positive contrast of worm hydrazides.
L. the 4-methyl isophthalic acid that contains of the present invention, 2, the bishydrazide derivative of 3-thiadiazoles group is to the mensuration of mosquito larvae insecticidal activity:
The 4-methyl isophthalic acid that contains of the present invention, 2, the bishydrazide derivative of 3-thiadiazoles group is as follows to the screening method of the insecticidal activity of mosquito larvae: culex pipiens pallens (Culex pipiens pallens), the normal population of indoor feeding; Take by weighing test compound about 2 milligrams in the penicillin medicine bottle, add 10 milliliters of acetone, vibration dissolving sample is mixed with the mother liquor of 200 mcg/ml; Pipette 1 milliliter of mother liquor in 100 ml beakers that fill 99 ml waters, choose mosquito larvae at the beginning of 10 4 ages, pour in the lump in the beaker together with 10 milliliters of feeding liquids, the concentration of its soup is 2 mcg/ml.It is 25 degrees centigrade of cultivations that the solution of handling well is put into indoor maintenance temperature together with the beaker of mosquito larvae, and check result after 24 hours observes till all larvae pupations.With the aqueous solution that contains 1 milliliter of acetone is blank; Add a small amount of mosquito feed and sucking-off tumbler every day, and moisture evaporated (5 milliliters/day) in the additional beaker, all dead or pupate up to mosquito larvae; Most larvas generally pupated in 8 days; With the positive contrast of worm hydrazides.
M. contain the 4-methyl isophthalic acid, 2, the mensuration that the bishydrazide derivative of 3-thiadiazoles group influences the pathogenic fungi growth activity:
The 4-methyl isophthalic acid that contains of the present invention, 2, the mensuration of the bishydrazide derivative bacteriostatic activity of 3-thiadiazoles group adopts thalli growth rate assay method, detailed process is: get 5 milligrams of sample dissolution in an amount of dimethyl formamide, then with containing the medicament that a certain amount of polysorbas20 emulsifier aqueous solution is diluted to 500 mcg/ml, reagent agent is respectively drawn under aseptic condition in 1 milliliter of injection culture dish, add 9 milliliters of substratum more respectively, make 50 mcg/ml pastille flat boards after shaking up, do blank with the flat board that adds 1 milliliter of aqua sterilisa, punch tool with 4 millimeters of diameters cuts the bacterium dish along the mycelia outer rim, move on the pastille flat board, being equilateral triangle puts, every processing repeats 3 times, culture dish is placed in the 24+1 degree centigrade of constant incubator cultivates, colony diameter to be contrasted expands to 2-3 centimetre of " Invest, Then Investigate " and respectively handles bacterium dish expansion diameter, average, relatively calculate relative bacteriostasis rate with blank, comprise frequently seen plants pathogenic bacteria on the various agricultural for the examination bacterial classification, its title and code name comprise AS: tomato early blight bacterium (Alternaria solani); BC: botrytis cinerea pers (Botrytis cinerea); CA: peanut Cercospora bacteria (Cercospora arachidicola); CB: sugar beet leaf spot bacteria (Cercospora beticola); CL: watermelon anthrax bacteria: (Colletotrichum lagenarium); FO: cucumber fusarium axysporum (Fusarium oxysporum); GZ: fusarium graminearum (Gibberella zeae); PG: rice blast fungus (Phyricularia grisea (Cooke) Sacc.); PI: phytophthora infestans (Phytophthora infestans (Mont.) de Bary); PP: ring rot of apple bacterium (Physalospora piricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); RS: dry thread Pyrenomycetes (Rhizoctonia solani kuhn), these bacterial classifications have good representativeness, can represent the kind of most of pathogenic bacteria that the field takes place in the agriculture production.
N. the 4-methyl isophthalic acid that contains of the present invention, 2, the mensuration of the derivative induced anti-disease activity of bishydrazide of 3-thiadiazoles group:
The 4-methyl isophthalic acid that contains of the present invention, 2, the active screening method of the derivative induced tobacco resisting tobacco mosaic virus of the bishydrazide of 3-thiadiazoles group (TMV) is:
(1). standard plant activator: selecting tiadinil (TDL) (purity is greater than 99.5%) is the plant activator of standard;
(2). contain the 4-methyl isophthalic acid, 2, the active screening method of the anti-TMV of the derivative induced tobacco of bishydrazide of 3-thiadiazoles group: the mensuration of the direct antiviral activity that exsomatizes adopts half leaf method to carry out; It is common cigarette with the seedling age unanimity that live body is induced, 3 basins are one group, cigarette seedling respectively at inoculation pre-treatment in preceding 7 days, processing mode comprises: spray test compound solution 2 to 3 times, each 10 milliliters, or soil treatment, each 10 milliliters, the 7th day frictional inoculation TMV on the tobacco leaf that newly grows, the cigarette seedling is placed its growth optimal temperature and illumination, and cultivation is after 3 days down, and inspection incidence, comprehensive scab number are calculated as follows out the inducing anti-disease toxic effect fruit of test compound to TMV, 3 repetitions are established in each processing, and water and TDL are selected in blank and the contrast of standard medicament respectively:
Wherein, R is the induce effect of new compound to the anti-TMV of tobacco, unit: %
CK is the average withered spot number of clear water contrast blade, unit: individual
I is for inducing the average withered spot number of handling rear blade, unit: individual through compound.
The invention has the beneficial effects as follows: the present invention is to containing the 4-methyl isophthalic acid, 2, the bishydrazide of 3-thiadiazoles group has carried out the optimization of first guide structure, and the synthetic new compound carried out the mensuration of desinsection, antibacterial and inducing anti-disease activity and anti-phytoviral activity, this compounds can be used for disease, insect pest and the virus disease control in agriculture field, field of forestry, gardening field.
The present invention will contain the 4-methyl isophthalic acid by specific preparation and biological activity determination and with formulation that commercially available agricultural chemical is used in combination complete processing and selection for embodiment more specifically describes, 2, synthetic and the biological activity and the application thereof of the bishydrazide derivative of 3-thiadiazoles group, but described embodiment only is used for specific description the present invention and unrestricted the present invention, especially its biological activity and complete processing only illustrate, and unrestricted this patent, embodiment is as follows:
Embodiment 1:4-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-5-formyl chloride
4-methyl isophthalic acid with 9.66 gram (0.067 mole) synthetic or purchase, 2,3-thiadiazoles-5-formic acid and 29 milliliters of thionyl chlorides join in 100 milliliters of three mouthfuls of round-bottomed flasks, and 80 degrees centigrade of following reflux 6 hours remove excessive thionyl chloride under reduced pressure, underpressure distillation collect 2000Pa, cut under 94-96 degree centigrade gets weak yellow liquid 9.25 gram column chromatography purifications, productive rate: 85%, and intermediate 4-methyl isophthalic acid, 2, the 3-thiadiazoles-sealing of 5-formyl chloride is kept in the moisture eliminator standby.
The preparation of embodiment 2:N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine
In 1000 milliliters of round-bottomed flasks, add 400 mmole tertiary butyl hydrazonium salt hydrochlorates; add 450 milliliters of methylene dichloride and 100 ml waters and 600 mmole sodium hydroxide again; under induction stirring and ice bath cooling, slowly drip 400 mmole 4-methyl isophthalic acids; 2; 50 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride; dropwise the back room temperature reaction 5 hours; the stopped reaction afterreaction mixes nothing and washes with water; tell organic layer; behind the anhydrous magnesium sulfate drying; removal of solvent under reduced pressure obtains N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-and N '-tertiary butyl hydrazine, product need not purifying can be directly used in next step reaction, carries out next step reaction behind the also available ethyl alcohol recrystallization.
Embodiment 3: replace the preparation of acyl chlorides
The substituted carboxylic acid that adds 0.2 mole in 50 milliliters of round-bottomed flasks adds 1.2 moles sulfur oxychloride again, and with oil bath reflux 3-4 hour, air distillation must replace acyl chlorides after removing the intact sulfur oxychloride of unreacted with reaction mixture, and sealing is preserved standby.
The preparation of embodiment 4:N-(substituted formacyl)-N '-tertiary butyl hydrazine
In 100 milliliters of round-bottomed flasks, add 15 mmole tertiary butyl hydrazonium salt hydrochlorates; add 30 milliliters of methylene dichloride and 5 ml waters and 3 mmole sodium hydroxide again; under induction stirring and ice bath cooling, slowly drip 20 milliliters of dichloromethane solutions of 15 mmole substituted formyl chlorine; dropwise the back room temperature reaction 3 hours; the stopped reaction afterreaction mixes nothing and washes with water; tell organic layer; behind the anhydrous magnesium sulfate drying; removal of solvent under reduced pressure obtains N-(substituted formacyl)-N '-tertiary butyl hydrazine; product need not purifying can be directly used in next step reaction, carries out next step reaction behind the also available ethyl alcohol recrystallization.
Embodiment 5: the synthetic and structure of target compound YZK-6-32 is identified (I-1)
Get 0.02 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.03 mole of triethylamine then; the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.02 mole of Benzoyl chloride, after dropwising down; room temperature continues to stir after 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 2.83%, fusing point: 200-202 degree centigrade
1H NMR (solvent: CDCl
3, chemical shift): 8.15 (s, 1H, NH), 7.29-7.37 (m, 5H, ArH), 2.51 (s, 3H, thiadiazolyl-CH
3), 1.56 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 319.1223 (M+H)
+
Embodiment 6: the synthetic and structure of target compound YZK-6-40 is identified (I-2)
Get 0.004 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.006 mole of triethylamine then; the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.004 mole of 2-methyl benzoyl chloride, after dropwising down; room temperature continues to stir after 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 32.34%, fusing point: 194-196 degree centigrade
1HNMR (solvent: CDCl
3, chemical shift): 7.94 (s, 1H, NH), 7.06-7.24 (m, 4H, ArH), 2.92 (s, 3H, ArCH
3), 2.50 (s, 3H, thiadiazolyl-CH
3), 1.57 (s, 9H, C (CH
3)
3), this compound
1The HNMR data presentation is consistent with its chemical structure, HR MS (m/z): 333.1380 (M+H)
+
Embodiment 7: the synthetic and structure of target compound YZK-6-42 is identified (I-3)
Get 0.005 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.015 mole of triethylamine then; the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.005 mole of 3-methyl benzoyl chloride, after dropwising down; room temperature continues to stir after 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous magnesium sulfate drying, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 43.32%, fusing point: 195-196 degree centigrade
1H NMR (solvent: CDCl
3, chemical shift): 7.77 (s, 1H, NH), 7.11-7.33 (m, 4H, ArH), 2.92 (s, 3H, ArCH
3), 2.57 (s, 3H, thiadiazolyl-CH
3), 1.57 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 333.1380 (M+H)
+
Embodiment 8: the synthetic and structure of target compound YZK-6-45 is identified (I-4)
Get 0.005 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.015 mole of triethylamine then; the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.005 mole of 4-methyl benzoyl chloride, after dropwising down; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous magnesium sulfate drying, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 43.92%, fusing point: 208-210 degree centigrade
1HNMR (solvent: CDCl
3, chemical shift): 7.77 (s, 1H, NH), 7.11-7.33 (m, 4H, ArH), 2.92 (s, 3H, ArCH
3), 2.57 (s, 3H, thiadiazolyl-CH
3), 1.57 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 333.1380 (M+H)
+
Embodiment 9: the synthetic and structure of target compound YZK-7-42 is identified (I-5)
Get 0.0071 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.0075 mole of triethylamine then; the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.0075 mole of 2-methoxy benzoyl chloride, after dropwising down; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous magnesium sulfate drying, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 43.82%, fusing point: 228-230 degree centigrade
1HNMR (solvent: CDCl
3, chemical shift): 8.27 (s, 1H, NH), 6.86-7.40 (m, 4H, ArH), 3.91 (s, 3H, OCH
3), 2.59 (s, 3H, thiadiazolyl-CH
3), 1.59 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 371.1148 (M+Na)
+
Embodiment 10: the synthetic and structure of target compound ZQX-2-18 is identified (I-6)
In 50 milliliters of round-bottomed flasks, add 1.5 gram N-(4-methyl isophthalic acids, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine, 0.77 the triethylamine of gram, 30 milliliters of methylene dichloride stirring and dissolving, under condition of ice bath, slowly drip 15 milliliters of dichloromethane solutions that are dissolved with 1.21 gram 3-methoxy benzoyl chlorides then, dropwised in 1 hour, naturally heat up, stirring at room 5 hours, reaction mixture water are given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, the decompression precipitation, (eluent is 60-90 degree centigrade a sherwood oil: ethyl acetate volume ratio 3: 1), obtain white solid 0.50 gram with 200-300 order silica gel column chromatography, yield 22.95%, fusing point: 166-167 degree centigrade;
1HNMR (solvent: CDCl
3, chemical shift): 1.558 (s, 9H, CH
3), 2.560 (s, 3H, CH
3), 3.765 (s, 3H, CH
3), 6.880-6.915 (m, 3H, ArH), 7.200 (t, 1H, J=8.0Hz, Ph), 8.082 (s, 1H, NH), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 349.1329 (M+H)
+
Embodiment 11: the synthetic and structure of target compound YZK-6-41 is identified (I-7)
Get 0.0082 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.0247 mole of triethylamine then; the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.0082 mole of 4-methoxy benzoyl chloride, after dropwising down; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous magnesium sulfate drying, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 46%, fusing point: 176-177 degree centigrade
1H NMR (solvent: CDCl
3, chemical shift): 8.09 (s, 1H, NH), 6.78-7.37 (m, 4H, ArH), 3.79 (s, 3H, OCH
3), 2.58 (s, 3H, thiadiazolyl-CH
3), 1.55 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 371.1148 (M+Na)
+
Embodiment 12: the synthetic and structure of target compound YZK-7-35 is identified (I-8)
Get 0.0091 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.01 mole of triethylamine then; the ice bath cooling down; slowly drip 5 milliliters of dichloromethane solutions of 0.1 mmole 2-chloro-benzoyl chloride, after dropwising, room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior; anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, and re-crystallizing in ethyl acetate obtains product; yield: 52.95%
1H NMR (solvent: CDCl
3, chemical shift): 8.02 (s, 1H, NH), 7.22-7.39 (m, 4H, ArH), 2.59 (s, 3H, thiadiazolyl-CH
3), 1.59 (s, 9H, C (CH
3)
3), this compound
1The HNMR data presentation is consistent with its chemical structure, HR MS (m/z): 351.0688 (M-H)
-
Embodiment 13: the synthetic and structure of target compound YZK-7-38 is identified (I-9)
Get 0.007 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.0074 mole of triethylamine then; the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.0074 mole of 3-chloro-benzoyl chloride, after dropwising down; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 45.65%, fusing point: 202-204 degree centigrade
1H NMR (solvent: CDCl
3, chemical shift): 7.95 (s, 1H, NH), 7.27-7.38 (m, 4H, ArH), 2.61 (s, 3H, thiadiazolyl-CH
3), 1.57 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 351.0688 (M-H)
-
Embodiment 14: the synthetic and structure of target compound YZK-7-45 is identified (I-10)
Get 0.0047 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.0047 mole of triethylamine then; the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.0047 mole of 4-chloro-benzoyl chloride, after dropwising down; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 56.68%, fusing point: 194-197 degree centigrade
1H NMR (solvent: CDCl
3, chemical shift): 8.00 (s, 1H, NH), 7.34-7.53 (m, 4H, ArH), 2.59 (s, 3H, thiadiazolyl-CH
3), 1.56 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 353.0833 (M+H)
+
Embodiment 15: the synthetic and structure of target compound YZK-7-15 is identified (I-11)
Get 0.005 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.01 mole of triethylamine then; the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.0055 mole of 2-fluorobenzoyl chloride, after dropwising down; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 43.24%, fusing point: 125-128 degree centigrade
1HNMR (solvent: CDCl
3, chemical shift): 8.10 (s, 1H, NH), 6.99-7.52 (m, 4H, ArH), 2.58 (s, 3H, thiadiazolyl-CH
3), 1.58 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 337.1129 (M+H)
+
Embodiment 16: the synthetic and structure of target compound YZK-7-19-5 is identified (I-12)
Get 0.1 mmole N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.12 mmole triethylamine then; the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.1 mmole 3-fluorobenzoyl chloride, after dropwising down; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 56%, fusing point: 199-200 degree centigrade
1H NMR (solvent: CDCl
3, chemical shift): 8.45 (s, 1H, NH), 7.06-7.29 (m, 4H, ArH), 2.57 (s, 3H, thiadiazolyl-CH
3), 1.55 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure.
Embodiment 17: the synthetic and structure of target compound YZK-6-37 is identified (I-13)
Get 0.02 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.03 mole of triethylamine then; the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.02 mole of 4-fluorobenzoyl chloride, after dropwising down; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 1.34%, fusing point: 204-207 degree centigrade
1H NMR (solvent: CDCl
3, chemical shift): 7.64 (s, 1H, NH), 7.04-7.64 (m, 4H, ArH), 2.62 (s, 3H, thiadiazolyl-CH
3), 1.57 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 337.1129 (M+H)
+
Embodiment 18: the synthetic and structure of target compound WH-2-34 is identified (I-14)
Get 0.013 mole of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.028 mmole triethylamine then, the ice bath cooling down, slowly drip 5 milliliters of dichloromethane solutions of 0.014 mmole 2-trifluoromethyl benzoyl chloride, after dropwising, room temperature continues to stir after 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, and the Virahol recrystallization obtains the product column chromatography purification, productive rate: 23.49%, fusing point: 173-175 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 7.77 (s, 1H, NH), 7.11-7.33 (m, 4H, ArH), 2.69 (s, 3H, thiadiazolyl-CH
3), 1.57 (s, 9H, C (CH
3)
3), the 1H NMR data presentation of this compound is consistent with its chemical structure; HR MS (m/z): 409.0917 (M+Na)
+
Embodiment 19: the synthetic and structure of target compound WH-2-35 is identified (I-15)
Get 0.016 mole of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, join in 50 milliliters of round-bottomed flasks, add acid binding agent 0.034 mole of triethylamine then, the ice bath cooling down, slowly drip 5 milliliters of dichloromethane solutions of 0.017 mole of 3-trifluoromethyl benzoyl chloride, after dropwising, room temperature continues to stir 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, and the Virahol recrystallization obtains the product column chromatography purification, productive rate: 10%, fusing point: 165-168 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 7.77 (s, 1H, NH), 7.11-7.33 (m, 4H, ArH), 2.69 (s, 3H, thiadiazolyl-CH
3), 1.57 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure; HRMS (m/z): 409.0917 (M+Na)
+
Embodiment 20: the synthetic and structure of target compound WH-3-18 is identified (I-16)
Get 0.0080 mole of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, join in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0080 mole of triethylamine then, the ice bath cooling down, slowly drip 5 milliliters of dichloromethane solutions of 0.0096 mole of 4-trifluorobenzoyl chloride, after dropwising, room temperature continues to stir 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, and removal of solvent under reduced pressure behind the suction filtration, re-crystallizing in ethyl acetate obtain the product column chromatography purification, productive rate: 33.44%, fusing point: 186-189 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 8.121 (s, 1H, NH), 7.57 (d, 2H, ArH), 7.49 (d, 2H, ArH), 2.69 (s, 3H, thiadiazolyl-CH
3), 1.57 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure; HRMS (m/z): 409.0917 (M
+Na)
+
Embodiment 21: the synthetic and structure of target compound YZK-7-50-1 is identified (I-17)
Get 0.0071 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.0078 mole of triethylamine then; the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.0078 mole of 2-nitrobenzoyl chloride, after dropwising down; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 19.52%, fusing point: 119-123 degree centigrade
1HNMR (solvent: CDCl
3, chemical shift): 3.81 (s, 1H, NH), 7.52-7.529 (m, 4H, ArH), 2.99 (s, 3H, thiadiazolyl-CH
3), 1.20 (s, 9H, C (CH
3)
3), this compound
1The HNMR data presentation is consistent with its chemical structure, HR MS (m/z): 364.1074 (M+H)
+
Embodiment 22: the synthetic and structure of target compound YZK-7-48 is identified (I-18)
Get 0.008 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.0088 mole of triethylamine then; the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.0088 mole of 3-nitrobenzoyl chloride, after dropwising down; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 44.72%, fusing point: 202-205 degree centigrade
1H NMR (solvent: CDCl
3, chemical shift): 8.04 (s, 1H, NH), 7.54-8.25 (m, 4H, ArH), 2.63 (s, 3H, thiadiazolyl-CH
3), 1.61 (s, 9H, C (CH
3)
3), this compound
1The HNMR data presentation is consistent with its chemical structure, HR MS (m/z): 364.1074 (M+H)
+
Embodiment 23: the synthetic and structure of target compound WH-2-33 is identified (I-19)
Get 0.0057 mole of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.113 mole of triethylamine then, the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.0057 mole of 4-nitrobenzoyl chloride down, after dripping, room temperature continued to stir after 4 hours, and the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, the Virahol recrystallization obtains the product column chromatography purification, productive rate: 18.31%, and fusing point: 99-101 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 8.28 (d, 1H, ArH), 8.20 (d, 1H, ArH), 5.29 (s, 1H, NH), 2.69 (s, 3H, thiadiazolyl-CH
3), 1.57 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure.
Embodiment 24: the synthetic and structure of target compound YZK-7-11 is identified (I-20)
Get 0.01 mole of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.02 mole of triethylamine then, the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.01 mole of 4-ethylamino benzonitrile acyl chlorides down, after dripping, room temperature continued to stir after 4 hours, and the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, re-crystallizing in ethyl acetate obtains the product column chromatography purification, productive rate: 26%, and fusing point: 176-178 degree centigrade; HR MS (m/z): 347.1536 (M+H)
+
Embodiment 25: the synthetic and structure of target compound YZK-6-36 is identified (I-21)
Get 0.02 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.03 mole of triethylamine then, the ice bath cooling slowly drips 0.02 mole of 4-methyl isophthalic acid down; 2; 5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dropwising, room temperature continues to stir after 5 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior; anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, re-crystallizing in ethyl acetate; yield: 2.35%, HR MS (m/z): 341.0849.
Embodiment 26: the synthetic and structure of target compound YZK-6-39 is identified (I-22)
Get 0.004 mole of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, join in 50 milliliters of round-bottomed flasks, add acid binding agent 0.006 mole of triethylamine then, the ice bath cooling down, slowly drip 5 milliliters of dichloromethane solutions of 0.004 mole of furans-2-formyl chloride, after dropwising, room temperature continues to stir after 5 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, re-crystallizing in ethyl acetate, yield: 15%, fusing point: 124-128 degree centigrade; HR MS (m/z): (M+H)
+: 309.1016.
Embodiment 27: the synthetic and structure of target compound YZK-7-3 is identified (I-23)
Get 0.008 mole of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, join in 50 milliliters of round-bottomed flasks, add acid binding agent 0.024 mole of triethylamine then, the ice bath cooling down, slowly drip 5 milliliters of dichloromethane solutions of 0.008 mole of 2-(4-chloro-phenyl-)-3-methyl-butyryl chloride, after dropwising, room temperature continues to stir after 5 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, re-crystallizing in ethyl acetate, yield: 30.37%, fusing point: 182-185 degree centigrade; HR MS (m/z): (M+Na)
+: 431.1279.
Embodiment 28: the synthetic and structure of target compound YZK-7-6 is identified (I-24)
Get 0.01 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.03 mole of triethylamine then; the ice bath cooling down; slowly drip 5 milliliters of dichloromethane solutions of 0.01 mole of trichoroacetic chloride, after dropwising, room temperature continues to stir after 5 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior; anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, re-crystallizing in ethyl acetate; yield: 40.50%, fusing point: 48-50 degree centigrade.
Embodiment 29: the synthetic and structure of target compound YZK-7-16 is identified (I-25)
Get 0.005 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.01 mole of triethylamine then; the ice bath cooling down; slowly drip 5 milliliters of dichloromethane solutions of 0.0053 mole of chrysanthemum acyl chlorides, after dropwising, room temperature continues to stir after 5 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior; anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, re-crystallizing in ethyl acetate; yield: 49.45%, HR MS (m/z): (M+Na)
+: 387.1825.
Embodiment 30: the synthetic and structure of target compound YZK-7-17 is identified (I-26)
Get 0.005 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.01 mole of triethylamine then; the ice bath cooling down; slowly drip 5 milliliters of dichloromethane solutions of 0.0053 mole of dichloro chrysanthemum acyl chlorides, after dropwising, room temperature continues to stir after 5 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior; anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, re-crystallizing in ethyl acetate; yield: 60.32%, HR MS (m/z): (M+Na)
+: 405.0913.
Embodiment 31: the synthetic and structure of target compound WH-5-28 is identified (I-27)
Get 0.0023 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; add in 50 milliliters of round-bottomed flasks; add acid binding agent 0.0023 mole of triethylamine then; the ice bath cooling down; slowly drip 5 milliliters of dichloromethane solutions of 0.0046 mole of 4-fluorobenzene acetyl acyl chlorides, after dripping, room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior; anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 4: 1 column chromatography purifications of ethyl acetate volume ratio; productive rate: 64.35%
1H NMR (solvent: DMSO, chemical shift): 7.623 (s, 1H, NH), 7.083 (t, 2H, ArH), 7.001 (t, 2H, ArH), 3.597 (s, 2H, CH
2) 2.947 (s, 3H, thiadiazolyl-CH
3), 1.479 (s, 9H, C (CH
3)
3), HR MS (m/z): (M+Na)
+: 373.1105.
Embodiment 32: the synthetic and structure of target compound WH-2-32 is identified (I-28)
Get 0.0134 mole of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, join in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0268 mole of triethylamine then, the ice bath cooling slowly drips 0.0134 mole 2,5 milliliters of dichloromethane solutions of 6-dichlorobenzoyl chloride down, after dropwising, room temperature continued to stir after 4 hours, and the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, the Virahol recrystallization obtains the white products column chromatography purification, productive rate: 14.64%, and fusing point: 118-119 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 7.77 (s, 1H, NH), 7.11-7.33 (m, 3H, ArH), 2.69 (s, 3Hthiadiazolyl-CH
3), 1.57 (s, 9H, C (CH
3)
3), the 1H NMR data presentation of this compound is consistent with its chemical structure; HR MS (m/z): 387.0444 (M+H)
+
Embodiment 33: the synthetic and structure of target compound WH-3-15 is identified (I-31)
Get 0.0103 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; add in 50 milliliters of round-bottomed flasks; add acid binding agent 0.0052 mole of triethylamine then; the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.0052 mole of positive capryl(yl)chloride, after dropwising down; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; sherwood oil and 4: 1 column chromatography purifications of ethyl acetate volume ratio; productive rate: 20%, liquid
1H NMR (solvent: CDCl
3, chemical shift): 9.104 (s, 1H, NH), 2.938 (s, 3H, thiadiazolyl-CH
3), 2.278 (s, 3H ,-CH
3) 1.445 (s, 9H, C (CH
3)
3), 1.211 (m, 7H ,-CH), 0.846 (m, 5H ,-CH), this compound
1H NMR data presentation is consistent with its chemical structure; HR MS (m/z): 363.1825 (M+Na)
+
Embodiment 34: the synthetic and structure of target compound WH-3-21 is identified (I-32)
Get 0.0140 mole of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0140 mole of triethylamine, the ice bath cooling drips 0.0157 mole 3,5 milliliters of dichloromethane solutions of 5-dichlorobenzoyl chloride down, after dripping off, stirring at room 4 hours, reaction mixture water are given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 4: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 19.34%, fusing point: 149-152 degree centigrade;
1HNMR (solvent: CDCl
3, chemical shift): 8.236 (s, 1H, NH), 7.364 (m, 1H, ArH), 7.276 (s, 1H, ArH), 7.272 (s, 1H, ArH), 2.69 (s, 3H, thiadiazolyl-CH
3), 1.57 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure; HRMS (m/z): 409.0263 (M+Na)
+
Embodiment 35: the synthetic and structure of target compound WH-3-25 is identified (I-33)
Get 0.01 mole of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.01 mole of triethylamine then, the ice bath cooling slowly drips 0.0119 mole 3,5 milliliters of dichloromethane solutions of 5-dimethyl benzoyl chloride down, after dripping, room temperature continues to stir 4 hours, and the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 5: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 17.29%, fusing point: 197-200 degree centigrade;
1HNMR (solvent: CDCl
3, chemical shift): 7.854 (s, 1H, NH), 6.988-6.972 (m, 3H, ArH), 2.578 (s, 3H, thiadiazolyl-CH
3), 2.256 (s, 6H ,-CH
3), 1.57 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure; HR MS (m/z): 369.1356 (M+Na)
+
Embodiment 36: the synthetic and structure of target compound WH-4-18 is identified (I-34)
Get 0.001 mole of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, join in 50 milliliters of round-bottomed flasks, add acid binding agent 0.001 mole of triethylamine then, the ice bath cooling down, slowly drip 5 milliliters of dichloromethane solutions of 0.00105 mole of 3-(2-chloro-phenyl-)-5-methyl-isoxazole-4-formyl chloride, after dropwising, room temperature continues to stir 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 4: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 18%, fusing point: 78-81 degree centigrade;
1HNMR (solvent: CDCl
3, chemical shift): 7.572-7.119 (m, 4H, ArH), 6.542 (1H ,-NH), 2.661 (s, 3Hthiadiazolyl-CH
3), 2.655 (s, 3H ,-CH
3), 1.365 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 456.0869 (M+Na)
+
Embodiment 37: the synthetic and structure of target compound WH-4-30 is identified (I-35)
Get 0.0038 mole of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, join in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0045 mole of triethylamine then, the ice bath cooling slowly drips 0.0045 mole 2,5 milliliters of dichloromethane solutions of 4-dimethyl-1-phenylpyrazole-3-formyl chloride down, after dropwising, room temperature continues to stir 4 hours, and the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 5: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 15%, fusing point: 220-224 degree centigrade;
1HNMR (solvent: CDCl
3, chemical shift): 7.712 (s, 1H, NH), 7.472-7.287 (m, 5H, ArH), 2.578 (s, 3H, thiadiazolyl-CH
3), 2.350 (s, 3H ,-CH
3), 2.302 (s, 3H ,-CH
3), 1.57 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure.
Embodiment 38: the synthetic and structure of target compound WH-4-37 is identified (I-36)
Get 0.0078 mole of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, join in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0078 mole of triethylamine then, the ice bath cooling down, slowly drip 5 milliliters of dichloromethane solutions of 0.0117 mole of cyclohexyl formyl chloride, after dropwising, room temperature continues to stir 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 4: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 35%, fusing point: 162-164 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 7.712 (s, 1H, NH), 2.578 (s, 3H, thiadiazolyl-CH
3), 2.302 (s, 3H ,-CH
3), 1.57 (s, 9H, C (CH
3)
3), 1.82-1,60 (m, 11H,
), this compound
1H NMR data presentation is consistent with its chemical structure; HR MS (m/z): 325.1693 (M+H)
+
Embodiment 39: the synthetic and structure of target compound WH-5-11 is identified (I-37)
Get 0.0023 mole of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0023 mole of triethylamine then, the ice bath cooling slowly drips 0.0035 mole 3,5 milliliters of dichloromethane solutions of 6-dichloropyridine-2-formyl chloride down, after dripping, room temperature continues to stir 4 hours, and the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 3: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 35%, fusing point: 162-164 degree centigrade;
1H NMR (solvent: DMSO, chemical shift): 8.087 (d, 1H, Pyridine-H), 7.619 (d, 1H, Pyridine-H), 2.529 (s, 3H, thiadiazolyl-CH
3), 1.526 (s, 9H, C (CH
3)
3), HR MS (m/z): 410.0216 (M+Na)
+
Embodiment 40: the synthetic and structure of target compound WSX-44 is identified (I-38)
Get 0.0037 mole of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0045 mole of triethylamine then, the ice bath cooling down, slowly drip 5 milliliters of dichloromethane solutions of 0.0037 mole of 5-ethyl-1-methylpyrazole-3-formyl chloride, after dripping, room temperature continues to stir 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 3: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 46%, fusing point: 147-148 degree centigrade;
1HNMR (solvent: CDCl
3, chemical shift): 8.527 (S, 1H, NH), 6.601 (s, 1H ,-CH=), 3.634 (s, 3H ,-CH
3), 2.867 (s, 3H, thiadiazolyl-CH
3), 2.540 (q, 2H, CH
2), 1.574 (s, 9H, C (CH
3)
3), 1.236 (s, 3H ,-CH
3), HR MS (m/z): 351.1598 (M+H)
+
Embodiment 41: the synthetic and structure of target compound WH-4-40 is identified (I-39)
Get 0.0084 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.0084 mole of triethylamine then; the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.0169 mole of o-fluorobenzene chloride, after dropwising down; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; sherwood oil and 5: 1 column chromatography purifications of ethyl acetate volume ratio; re-crystallizing in ethyl acetate, productive rate: 33%
1H NMR (solvent: CDCl
3, chemical shift): 11.179 (s, 1H, NH), 7.299-7.113 (m, 4H, Ph), 2.857 (s, 3H, thiadiazolyl-CH
3), 2.504 (s, 2H, CH
2), 1.394 (s, 9H, C (CH
3)
3).
Embodiment 42: the synthetic and structure of target compound YZK-7-29 is identified (II-2)
Getting 0.1 mmole N-(2-methyl benzoyl)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.12 mmole triethylamine then; the ice bath cooling down; slowly drip 0.1 mmole 4-methyl isophthalic acid; 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride are after dropwising; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 13.03%, fusing point: 145-147 degree centigrade
1H NMR (solvent: CDCl
3, chemical shift): 5.74 (s, 1H, NH), 7.24-7.43 (m, 4H, ArH), 2.85 (s, 3H, ArCH
3), 2.41 (s, 3H, thiadiazolyl-CH
3), 1.21 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 333.1380 (M+H)
+
Embodiment 43: the synthetic and structure of target compound WH-4-6 is identified (II-3)
Get 0.0096 mole of N-(3-methyl benzoyl)-N '-tertiary butyl hydrazine and be dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0096 mole of triethylamine then, the ice bath cooling down, slowly drip 0.0192 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dripping, stirring at room 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 6: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 30%; Fusing point: 142-145 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 8.565 (s, 1H, NH), 7.080 (m, 4H, ArH), 2.623 (s, 3H, thiadiazolyl-CH
3), 2.352 (s, 3H ,-CH
3), 1.579 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure; HR MS (m/z): 333.1380 (M+H)
+
Embodiment 44: the synthetic and structure of target compound YZK-6-48 is identified (II-4)
Getting 0.1 mmole N-(4-methyl benzoyl)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.12 mmole triethylamine then; the ice bath cooling down; slowly drip 0.1 mmole 4-methyl isophthalic acid; 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride are after dropwising; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 6.02%, fusing point: 143-144 degree centigrade
1HNMR (solvent: CDCl
3, chemical shift): 7.31-7.80 (m, 4H, ArH), 5.74 (s, 1H, NH), 2.92 (s, 3H, ArCH
3), 2.46 (s, 3H, thiadiazolyl-CH
3), 1.18 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 333.1380 (M+H)
+
Embodiment 45: the synthetic and structure of target compound YZK-7-44 is identified (II-5)
Getting 0.1 mmole N-(2-anisoyl)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.12 mmole triethylamine then; the ice bath cooling down; slowly drip 0.1 mmole 4-methyl isophthalic acid; 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride are after dropwising; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 34.85%, fusing point: 141-142 degree centigrade
1HNMR (solvent: CDCl
3, chemical shift): 9.52 (s, 1H, NH), 6.70-8.02 (m, 4H, ArH), 4.01 (s, 3H, OCH
3), 2.86 (s, 3H, thiadiazolyl-CH
3), 1.59 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 371.1148 (M+Na)
+
Embodiment 46: the synthetic and structure of target compound ZQX-2-20-b is identified (II-6)
In 100 milliliters of round-bottomed flasks, add 2.9 gram tertiary butyl hydrazonium salt hydrochlorates, 1.0 gram NaOH, 30 milliliters methylene dichloride, 1 ml water stirs.Under condition of ice bath, slowly drip 15 milliliters of dichloromethane solutions that contain 1.98 gram 3-methoxy benzoyl chlorides, finished in 30 minutes, stirring at room 5 hours, tell organic layer, wash with water 2 times, with anhydrous sodium sulfate drying 12 hours, suction filtration, rotary evaporation obtained the 2.2 gram intermediate N '-tertiary butyl-N-(3-methoxybenzoyl hydrazine).
In 100 milliliters of round-bottomed flasks, add the 0.0099 mole of N '-tertiary butyl-N-(3-methoxybenzoyl hydrazine), 0.1060 the triethylamine that rubs, 40 milliliters of methylene dichloride stirring and dissolving, under condition of ice bath, slowly drip then and be dissolved with the 0.0110 4-methyl isophthalic acid that rubs, 2,20 milliliters of the dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, dropwised in 1 hour, naturally heat up stirring at room 5 hours, decompression precipitation, (eluent is 60-90 degree centigrade a sherwood oil: ethyl acetate volume ratio 2: 1) with 200-300 order silica gel column chromatography, obtain white solid 0.70 gram, yield 20.29%, fusing point: 151-152 degree centigrade; 1HNMR (solvent: CDCl
3, chemical shift): 1.591 (s, 9H, CH
3), 2.809 (s, 3H, CH
3), 3809 (s, 3H, CH
3), 7.060-7.325 (m, 4H, ArH), 8.127 (s, 1H, NH); This compound
1The HNMR data presentation is consistent with its chemical structure, HRMS (m/z): 349.1329 (M+H)
+
Embodiment 47: the synthetic and structure of target compound WH-4-7 is identified (II-7)
Getting 0.0104 mole of N-(4-anisoyl)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, join in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0104 mole of triethylamine then, the ice bath cooling down, slowly drip 0.0208 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride are after dropwising, room temperature continues to stir 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying, removal of solvent under reduced pressure behind the suction filtration, obtain crude product, methylene dichloride and sherwood oil recrystallization, productive rate: 30%, fusing point: 135-137 degree centigrade; HR MS (m/z): 349.1329 (M+H)
+
Embodiment 48: the synthetic and structure of target compound YZK-7-34 is identified (II-8)
Getting 0.1 mmole N-(2-chlorobenzene formacyl)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.12 mmole triethylamine then; the ice bath cooling down; slowly drip 0.1 mmole 4-methyl isophthalic acid; 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride are after dropwising; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 20.36%, fusing point: 165-169 degree centigrade
1H NMR (solvent: CDCl
3, chemical shift): 8.15 (s, 1H, NH), 7.11-7.40 (m, 4H, ArH), 2.80 (s, 3H, thiadiazolyl-CH
3), 1.62 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 353.0833 (M+H)
+
Embodiment 49: the synthetic and structure of target compound YZK-7-39 is identified (II-9)
Getting 0.1 mmole N-(3-chlorobenzene formacyl)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.12 mmole triethylamine then; the ice bath cooling down; slowly drip 0.1 mmole 4-methyl isophthalic acid; 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride are after dropwising; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 40.49%, fusing point: 138-142 degree centigrade
1HNMR (solvent: CDCl
3, chemical shift): 8.33 (s, 1H, NH), 7.33-7.59 (m, 4H, ArH), 2.79 (s, 3H, thiadiazolyl-CH
3), 1.59 (s, 9H, C (CH
3)
3), this compound
1The HNMR data presentation is consistent with its chemical structure.
Embodiment 50: the synthetic and structure of target compound YZK-7-46 is identified (II-10)
Getting 0.1 mmole N-(4-chlorobenzene formacyl)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.12 mmole triethylamine then; the ice bath cooling down; slowly drip 0.1 mmole 4-methyl isophthalic acid; 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride are after dropwising; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 54.87%, fusing point: 137-139 degree centigrade
1H NMR (solvent: CDCl
3, chemical shift): 8.50 (s, 1H, NH), 7.37-7.56 (m, 4H, ArH), 2.76 (s, 3H, thiadiazolyl-CH
3), 1.58 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 353.0833 (M+H)
+
Embodiment 51: the synthetic and structure of target compound YZK-7-19-1 is identified (II-11)
Getting 0.1 mmole N-(2-fluoro benzoyl)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.12 mmole triethylamine then; the ice bath cooling down; slowly drip 0.1 mmole 4-methyl isophthalic acid; 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride are after dropwising; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 7.51%, fusing point: 109-109 degree centigrade
1HNMR (solvent: CDCl
3, chemical shift): 8.44 (s, 1H, NH), 7.12-7.92 (m, 4H, ArH), 2.84 (s, 3H, thiadiazolyl-CH
3), 1.60 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 337.1129 (M+H)
+
Embodiment 52: the synthetic and structure of target compound YZK-7-31 is identified (II-12)
Getting 0.1 mmole N-(3-fluoro benzoyl)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.12 mmole triethylamine then; the ice bath cooling down; slowly drip 0.1 mmole 4-methyl isophthalic acid; 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride are after dropwising; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 63.33%, fusing point: 212-213 degree centigrade
1H NMR (solvent: CDCl
3, chemical shift): 8.59 (s, 1H, NH), 7.22-7.40 (m, 4H, ArH), 2.76 (s, 3H, thiadiazolyl-CH
3), 1.58 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 337.1129 (M+H)
+
Embodiment 53: the synthetic and structure of target compound WH-3-43-B is identified (II-13)
Get 0.0133 mole of N-(4-fluoro benzoyl)-N '-tertiary butyl hydrazine and be dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0133 mole of triethylamine then, the ice bath cooling down, slowly drip 0.0139 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dripping, stirring at room 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 5: 1 column chromatography purifications of ethyl acetate volume ratio, fusing point: 162-164 degree centigrade, productive rate: 30%;
1H NMR (solvent: CDCl
3, chemical shift): 8.565 (s, 1H, NH), 7.635 (d, 2H, ArH), 7.080 (d, 2H, ArH), 2.623 (s, 3H, thiadiazolyl-CH
3), 1.579 (s, 9H, CH
3), this compound
1H NMR data presentation is consistent with its chemical structure; HR MS (m/z): 337.1129 (M+H)
+
Embodiment 54: the synthetic and structure of target compound WH-3-32 is identified (II-14)
Getting 0.0057 mole of N-(2-trifluoromethyl benzoyl)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, join in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0057 mole of triethylamine then, the ice bath cooling down, slowly drip 0.0060 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dropwising, room temperature continues to stir 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and ethyl acetate volume ratio 5: 1 and sherwood oil and 4: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 20%, fusing point: 198-199 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 8.094 (s, 1H, NH), 7.117 (m, 4H, ArH), 2.623 (s, 3H, thiadiazolyl-CH
3) 1.558 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure.
Embodiment 55: the synthetic and structure of target compound WH-3-33 is identified (II-15)
Get 0.0088 mole of N-(3-trifluoromethyl benzoyl)-N '-tertiary butyl hydrazine and be dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0088 mole of triethylamine then, the ice bath cooling down, slowly drip 0.0093 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dropwising, room temperature continues to stir 4 hours, and the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration obtains white solid yield 28.24%, fusing point: 200-203 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 8.554 (s, 1H, NH), 7.887 (s, 1H, ArH), 7.775 (q, 2H, ArH), 7.558 (t, 1H, ArH), 2.623 (s, 3H, thiadiazolyl-CH
3), 1.558 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure; HR MS (m/z): 387.1097 (M+H)
+
Embodiment 56: the synthetic and structure of target compound WH-3-22 is identified (II-16)
Get 0.01535 mole of N-(4-trifluoromethyl benzoyl)-N '-tertiary butyl hydrazine and be dissolved in 20 milliliters of methylene dichloride, add 50 milliliters of round-bottomed flasks, add acid binding agent 0.01535 mole of triethylamine, the ice bath cooling down, slowly drip 0.01842 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dripping, stirring at room 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying, removal of solvent under reduced pressure, sherwood oil and ethyl acetate and methylene chloride volume were than 5: 1: 1 column chromatography purifications, productive rate: 46.28%, fusing point: 149-151 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 8.485 (s, 1H, NH), 7.688 (m, 4H, ArH), 2.623 (s, 3H, thiadiazolyl-CH
3), 1.558 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure; HR MS (m/z): 387.1097 (M+H)
+
Embodiment 57: the synthetic and structure of target compound WH-4-12 is identified (II-17)
Get 0.0059 mole of N-(2-nitro benzoyl)-N '-tertiary butyl hydrazine and be dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0062 mole of triethylamine then, the ice bath cooling down, slowly drip 0.0062 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dripping, room temperature continues to stir 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 4: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 25%, fusing point: 193-195 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 8.229 (s, 1H, ArH), 8.026 (s, 1H, ArH), 7.564-7.530 (m, 2H, ArH), 6.397 (s, 1H, NH), 2.560 (s, 3H, CH
3), 1.558 (s, 9H ,-C (CH
3)
3), this compound
1The HNMR data presentation is consistent with its chemical structure; HRMS (m/z): 364.1074 (M+H)
+
Embodiment 58: the synthetic and structure of target compound YZK-7-49 is identified (II-18)
Getting 0.1 mmole N-(3-nitro benzoyl)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.12 mmole triethylamine then; the ice bath cooling down; slowly drip 0.1 mmole 4-methyl isophthalic acid; 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride are after dropwising; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 53.65%, fusing point: 167-176 degree centigrade
1HNMR (solvent: CDCl
3, chemical shift): 9.05 (s, 1H, NH), 7.64-8.46 (m, 4H, ArH), 2.78 (s, 3H, thiadiazolyl-CH
3), 1.61 (s, 9H, C (CH
3)
3), this compound
1The HNMR data presentation is consistent with its chemical structure, HR MS (m/z): 364.1074 (M+H)
+
Embodiment 59: the synthetic and structure of target compound YZK-6-50 is identified (II-19)
Getting 0.1 mmole N-(4-nitro benzoyl)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.12 mmole triethylamine then; the ice bath cooling down; slowly drip 0.1 mmole 4-methyl isophthalic acid; 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride are after dropwising; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; re-crystallizing in ethyl acetate obtains product; yield: 20.23%, fusing point: 152-155 degree centigrade
1HNMR (solvent: CDCl
3, chemical shift): 8.78 (s, 1H, NH), 7.76-8.25 (m, 4H, ArH), 2.77 (s, 3H, thiadiazolyl-CH
3), 1.59 (s, 9H, C (CH
3)
3), this compound
1The HNMR data presentation is consistent with its chemical structure, HR MS (m/z): 364.1074 (M+H)
+
Embodiment 60: the synthetic and structure of target compound YZK-7-33 is identified (II-20)
Getting 0.01 mole of N-(4-ethylamino benzonitrile acyl group)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.015 mole of triethylamine then; the ice bath cooling down; slowly drip 0.015 mole of 4-methyl isophthalic acid; 2; 5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dropwising, room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior; anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, and re-crystallizing in ethyl acetate obtains product; yield: 10.41%, HR MS (m/z): 347.1536 (M+H)
+
Embodiment 61: the synthetic and structure of target compound YZK-7-4 is identified (II-23)
Getting 0.005 mole of N-(2-(4-chloro-phenyl-)-3-methyl-butyryl radicals)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.015 mole of triethylamine then; the ice bath cooling down; slowly drip 0.005 mole of 4-methyl isophthalic acid; 2; 5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dropwising, room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior; anhydrous magnesium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, and re-crystallizing in ethyl acetate obtains product; yield: 32.36%, HR MS (m/z): 409.1460 (M+H)
+
Embodiment 62: the synthetic and structure of target compound WH-3-10 is identified (II-25)
Get 0.0204 mole of freshly prepd N-(chrysanthemum acyl group)-N '-tertiary butyl hydrazine and be dissolved in 20 milliliters of methylene dichloride, add 50 milliliters of round-bottomed flasks, add acid binding agent 0.0306 mole of triethylamine then, the ice bath cooling down, slowly drip 0.0306 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dripping, room temperature continues to stir 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 6: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 10%, fusing point: 153-155 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 4.846 (s, 1H, NH), 2.818 (d, 3H, thiadiazolyl-CH
3), 1.701 (s, 3H ,-CH
3), 1.660 (s, 3H ,-CH
3), 1.570 (s, 3H ,-CH
3), 1.541 (s, 3H ,-CH
3), 1.528 (s, 9H, C (CH
3)
3), 1.125 (s, 1H ,-CH), 1.027 (s, 1H ,-CH), 0.748 (s, 1H ,-CH), this compound
1H NMR data presentation is consistent with its chemical structure; HR MS (m/z): 387.1825 (M+Na)
+
Embodiment 63: the synthetic and structure of target compound WH-3-14 is identified (II-26)
Get 0.0197 mole of freshly prepd N-(dichloro chrysanthemum acyl group)-N '-tertiary butyl hydrazine and be dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0197 mole of triethylamine then, the ice bath cooling down, slowly drip 0.0207 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dropwising, room temperature continues to stir 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 6: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 35.13%, fusing point: 146-148 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 7.527 (s, 1H, NH), 5.597 (m, 1H ,=CH), 2.806 (d, 3H, thiadiazolyl-CH
3), 2.235 (m, 1H ,-CH), 1.534 (s, 9H, C (CH
3)
3), 1.240 (t, 2H ,-CH
2), 1.162 (t, 2H ,-CH
3), 1.072 (s, 1H ,-CH), 0.762 (s, 1H ,-CH), 0.070 (s, 2H ,-CH), this compound
1H NMR data presentation is consistent with its chemical structure; HRMS (m/z): 427.0722 (M+Na)
+
Embodiment 64: the synthetic and structure of target compound WSX-54 is identified (II-27)
Get 0.0013 mole of freshly prepd N-(4-fluorophenethyl acyl group)-N '-tertiary butyl hydrazine and be dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.002 mole of triethylamine then, the ice bath cooling down, slowly drip 0.0015 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dropwising, room temperature continues to stir 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 6: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 54%, fusing point: 200-202 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 7.621 (m, 2H, ArH), 7.092 (t, 2H, ArH), 2.788 (d, 3H, thiadiazolyl-CH
3), 2.174 (s, 2H ,-CH
2), 1.586 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure.
Embodiment 65: the synthetic and structure of target compound WH-3-42 is identified (II-28)
Get 0.0062 mole of N-(2,6-dichloro-benzoyl base)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0062 mole of triethylamine then, the ice bath cooling down, slowly drip 0.0065 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dripping, room temperature continues to stir 4 hours, and the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 5: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 22.43%, fusing point: 195-198 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 7.445-7.305 (m, 3H, ArH), 5.567 (s, 1H, NH), 2.623 (s, 3H, thiadiazolyl-CH
3), 1.236 (s, 9H, CH
3), this compound
1H NMR data presentation is consistent with its chemical structure; HR MS (m/z): 409.0263 (M+Na)
+
Embodiment 66: the synthetic and structure of target compound WH-2-39 is identified (II-29)
Getting 0.0047 mole of N-ethanoyl-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, join in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0094 mole of triethylamine then, the ice bath cooling down, slowly drip 0.0045 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dropwising, room temperature continues to stir 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, re-crystallizing in ethyl acetate column chromatography purification, productive rate: 33.81%, fusing point: 76-78 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 5.543 (s, 1H, NH), 3.028 (s, 3H ,-CH
3), 2.623 (s, 3H, thiadiazolyl-CH
3), 1.558 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure; HR MS (m/z): 279.0886 (M+Na)
+
Embodiment 67: the synthetic and structure of target compound WH-2-44 is identified (II-30)
Get 0.0109 mole of N-butyryl radicals-N '-tertiary butyl hydrazine and be dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0217 mole of triethylamine then, the ice bath cooling down, slowly drip 0.0217 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dropwising, room temperature continues to stir 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 3: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 27.50%, fusing point: 75-78 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 5.596 (s, 1H, NH), 3.051 (m, 1H ,-CH), 3.026 (s, 3H, thiadiazolyl-CH
3), 2.845 (m, 1H ,-CH), 1.762 (m, 2H ,-CH
2), 1.071 (s, 9H, C (CH
3)
3), 1.020 (t, 3H ,-CH
3), this compound
1H NMR data presentation is consistent with its chemical structure; HR MS (m/z): 285.1380 (M+H)
+
Embodiment 68: the synthetic and structure of target compound WH-4-14 is identified (II-31)
Getting 0.0293 mole of N-capryloyl-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.0323 mole of triethylamine then; the ice bath cooling down; slowly drip 0.0323 mole of 4-methyl isophthalic acid; 2; 5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dropwising, room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior; anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and ethyl acetate volume ratio 4: 1; productive rate: 33%
1H NMR (solvent: CDCl
3, chemical shift): 7.890 (s, 1H, NH), 2.787 (s, 3H, thiadiazolyl-CH
3), 2.026 (m, 2H ,-CH
2), 1.509 (s, 9H ,-C (CH
3)
3), 1.258-1.103 (m, 10H ,-CH
2), 0.857 (t, 3H, CH
3), this compound
1H NMR data presentation is consistent with its chemical structure; HR MS (m/z): 341.2006 (M+H)
+
Embodiment 69: the synthetic and structure of target compound WH-3-23 is identified (II-32)
Get 0.01169 mole of N-(3,5-dichloro-benzoyl base)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, join in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0123 mole of triethylamine then, the ice bath cooling down, slowly drip 0.0100 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride are after dropwising, stirring at room 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying, and removal of solvent under reduced pressure obtains the white mass column chromatography purification behind the suction filtration, productive rate: 49.73%, fusing point: 228-231 degree centigrade;
1HNMR (solvent: CDCl
3, chemical shift): 8.163 (s, 1H, NH), 7.540-7.531 (t, 1H, ArH), 7.446 (d, 2H, ArH), 2.623 (s, 3H, thiadiazolyl-CH
3), 1.558 (s, 9H, C (CH
3)
3), the 1H NMR data presentation of this compound is consistent with its chemical structure; HR MS (m/z): 387.0444 (M+H)
+
Embodiment 70: the synthetic and structure of target compound WH-3-27 is identified (II-33)
Get 0.0144 mole of N-(3, the 5-dimethylbenzoyl)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0144 mole of triethylamine then, the ice bath cooling down, slowly drip 0.0150 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dropwising, stirring at room 4 hours, reaction mixture water are given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 5: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 13.43%, fusing point: 182-185 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 8.094 (s, 1H, NH), 7.117 (m, 3H, ArH), 2.623 (s, 3H, thiadiazolyl-CH
3), 2.314 (s, 6H ,-CH
3), 1.558 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure; HR MS (m/z): 347.1536 (M+H)
+
Embodiment 71: the synthetic and structure of target compound WH-4-42 is identified (II-36)
Getting 0.0029 mole of N-(cyclohexylcarbonyl)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.0057 mole of triethylamine then; the ice bath cooling down; slowly drip 0.0057 mole of 4-methyl isophthalic acid; 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride are after dropwising; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying, removal of solvent under reduced pressure behind the suction filtration; sherwood oil and methylene dichloride recrystallization; fusing point: 182-185 degree centigrade, productive rate: 25%
1H NMR (solvent: CDCl
3, chemical shift): 7.712 (s, 1H, NH), 2.578 (s, 3H, thiadiazolyl-CH
3), 2.302 (s, 3H ,-CH
3), 1.57 (s, 9H, C (CH
3)
3), 1.82-1.60 (m, 11H,
), this compound
1H NMR data presentation is consistent with its chemical structure; HR MS (m/z): 325.1693 (M+H)
+
Embodiment 72: the synthetic and structure of target compound WSX-50 is identified (II-38)
Get 0.0144 mole of N-(1 methyl-5-ethyl pyrazoles-3-formyl radical)-N '-tertiary butyl hydrazine and be dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0144 mole of triethylamine then, the ice bath cooling down, slowly drip 0.0150 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dropwising, room temperature continues to stir 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 5: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 13.43%, fusing point: 182-185 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 8.094 (s, 1H, NH), 7.117 (m, 3H, ArH), 2.623 (s, 3H, thiadiazolyl-CH
3), 2.314 (s, 6H ,-CH
3), 1.558 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure; HR MS (m/z): 347.1536 (M+H)
+
Embodiment 73: the synthetic and structure of target compound WH-2-36 is identified (III-1)
Get 0.01 mole of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, join in 50 milliliters of round-bottomed flasks, add acid binding agent 0.02 mole of triethylamine then, the ice bath cooling down, slowly drip 5 milliliters of dichloromethane solutions of 0.01 mole of Acetyl Chloride 98Min., after dropwising, room temperature continues to stir 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 3: 1 column chromatography purifications of ethyl acetate volume ratio, productive rate: 48.93%, fusing point: 113-114 degree centigrade;
1H NMR (solvent: CDCl
3, chemical shift): 2.69 (s, 3H, thiadiazolyl-CH
3), 2.587 (s, 3H ,-CH
3), 2.029 (s, 3H ,-CH
3), 1.57 (s, 9H, C (CH
3)
3), this compound
1The HNMR data presentation is consistent with its chemical structure; HRMS (m/z): 321.0992 (M+Na)
+
Embodiment 74: the synthetic and structure of target compound WH-2-43 is identified (III-2)
Get 0.009 mole of N-(4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; join in 50 milliliters of round-bottomed flasks; add acid binding agent 0.0054 mole of triethylamine then; the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.027 mole of butyryl chloride, after dropwising down; room temperature continues to stir 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration; sherwood oil and 3: 1 column chromatography purifications of ethyl acetate volume ratio; productive rate: 45.76%, liquid
1H NMR (solvent: CDCl
3, chemical shift): 2.936 (s, 3H, thiadiazolyl-CH
3), 2.849 (s, 2H ,-CH), 2.157 (m, 1H ,-CH), 2.049 (m, 1H ,-CH), 1.714 (m, 4H ,-CH2), 1.348 (s, 9H, C (CH
3)
3), 1.021 (t, 3H ,-CH
3), 0.928 (t, 3H ,-CH
3), this compound
1H NMR data presentation is consistent with its chemical structure.
Embodiment 75: target compound: the synthetic and structure of ZQX-2-20-a is identified (IV-1)
In 100 milliliters of round-bottomed flasks, add 0.0099 N-(3-the anisoyl)-N '-tertiary butyl hydrazine that rubs, 0.1060 the triethylamine that rubs, 40 milliliters of methylene dichloride stirring and dissolving, under condition of ice bath, slowly drip then and be dissolved with the 0.0110 4-methyl isophthalic acid that rubs, 2,20 milliliters of the dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, dropwised in 1 hour, naturally heat up stirring at room 5 hours, decompression precipitation, (eluent is 60-90 degree centigrade a sherwood oil: ethyl acetate volume ratio 3: 1) with 200-300 order silica gel column chromatography, obtain white solid 0.42 gram, yield 12.17%, fusing point: 127-128 degree centigrade;
1HNMR (solvent: CDCl
3, chemical shift): 1.189 (s, 9H, CH
3), 2.910 (s, 3H, CH
3), 3.871 (s, 3H, CH
3), 5.702 (s, 1H, NH), 7.166-7.442 (m, 4H, ArH), this compound
1H NMR data presentation is consistent with its chemical structure, HR MS (m/z): 349.1329 (M+H)
+
Embodiment 76: the synthetic and structure of target compound WH-3-43-A is identified (IV-2)
Get 0.0133 mole of N-(4-fluoro benzoyl)-N '-tertiary butyl hydrazine and be dissolved in 20 milliliters of methylene dichloride, add in 50 milliliters of round-bottomed flasks, add acid binding agent 0.0133 mole of triethylamine then, the ice bath cooling down, slowly drip 0.0139 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, after dripping, stirring at room 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying, removal of solvent under reduced pressure behind the suction filtration, sherwood oil and 5: 1 column chromatography purifications of ethyl acetate volume ratio, fusing point: 168-171 degree centigrade, productive rate: 10%;
1H NMR (solvent: CDCl
3, chemical shift): 7.922-7.887 (q, 2H, ArH), 7.221-7.179 (t, 2H, ArH), 5.743 (s, 1H, NH), 2.623 (s, 3H, thiadiazolyl-CH
3), 1.579 (s, 9H, C (CH
3)
3), this compound
1H NMR data presentation is consistent with its chemical structure; HR MS (m/z): 337.1129 (M+H)
+
Embodiment 77: the synthetic and structure of target compound WH-5-16 is identified (V-1)
Get the N-(3 of 0.00454 mole of preparation; 6-dichloropyridine-2-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; add in 50 milliliters of round-bottomed flasks; add acid binding agent 0.0068 mole of triethylamine then; the ice bath cooling down; slowly drip 0.0068 mole of 4-methyl isophthalic acid, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride; after dripping; room temperature continues to stir 4 hours, and the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying; removal of solvent under reduced pressure behind the suction filtration; sherwood oil and methylene dichloride mixed solvent recrystallization, productive rate: 30%
1HNMR (solvent: CDCl
3, chemical shift): 7.557 (d, 1H, ArH), 7.209 (d, 1H, ArH), 2.795 (s, 3H, thiadiazolyl-CH
3), 2.590 (s, 3H ,-CH
3), 1.645 (s, 9H, C (CH
3)
3), HR MS (m/z): 536.0103 (M+Na)
+
Embodiment 78: the synthetic and structure of target compound WSX-40 is identified (VI-1)
Get 0.007 mole of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, add in 100 milliliters of round-bottomed flasks, add acid binding agent 0.008 mole of triethylamine then, the ice bath cooling down, slowly drip 5 milliliters of dichloromethane solutions of 0.0035 mole of p-phthaloyl chloride, after dripping, room temperature continues to stir 4 hours, the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying spends the night, removal of solvent under reduced pressure behind the suction filtration, and sherwood oil and methylene dichloride recrystallization get product, productive rate: 21%, fusing point is greater than 250 degrees centigrade;
1HNMR (solvent: CDCl
3, chemical shift): 11.058 (s, 1H, NH), 11.011 (s, 1H, NH), 7.407 (s, 2H, ArH), 2.391 (s, 6H, thiadiazolyl-CH
3), 1.464 (s, 18H, C (CH
3)
3), HR MS (m/z): 581.1724 (M+Na)
+
Embodiment 79: the 4-methyl isophthalic acid that contains of the present invention, 2, the insecticidal activity of the bishydrazide derivative of 3-thiadiazoles group
Bioassay results sees Table 2, table 2 shows, synthetic major part of the present invention contains the 4-methyl isophthalic acid, 2, the bishydrazide compounds of 3-thiadiazoles group has excellent insecticidal activity, activity for small cabbage moth: when 400 mcg/ml, the insecticidal activity of the positive control medicament worm hydrazides of the insecticidal activity of Compound I-5, I-7, I-18, I-23, I-27, I-34, I-35, I-36, I-39, II-7, II-10, II-14, II-36 and IV-1, IV-2, V-1, VI-1 and homogeneous structure quite or be higher than the insecticidal activity of positive control medicament worm hydrazides; When 200 mcg/ml, the insecticidal activity of the positive control medicament worm hydrazides of the insecticidal activity of Compound I-4, I-6, I-7, I-8, I-10, I-11, I-12, I-14, I-15, I-20, I-21, I-22, I-24, I-25, I-26, I-32, I-38, II-2, II-3, II-4, II-5, II-8, II-9, II-12, II-15, II-16, II-17, II-18, II-19, II-23, II-29, II-38 and III-1, III-2 and homogeneous structure quite or be higher than the insecticidal activity of positive control medicament worm hydrazides; For mosquito larvae, when 2 mcg/ml, the insecticidal activity of the positive control medicament worm hydrazides of the insecticidal activity of Compound I-1, I-10, I-15, I-22, I-31, I-38 and II-2, II-13, II-15, II-16, II-20, II-25, II-28, II-31 and homogeneous structure quite or be higher than the insecticidal activity of positive control medicament worm hydrazides.The activity of part of compounds has reached 100%, and is outstanding especially, is significantly higher than the positive control medicament.
Embodiment 80: the 4-methyl isophthalic acid that contains of the present invention, 2, the bacteriostatic activity of the bishydrazide derivative of 3-thiadiazoles group
The title and the code name of frequently seen plants pathogenic fungi comprise AS on the agricultural of the present invention's test: tomato early blight bacterium (Alternaria solani); BC: botrytis cinerea pers (Botrytis cinerea); CA: peanut Cercospora bacteria (Cercosporaarachidicola); CB: sugar beet leaf spot bacteria (Cercospora beticola); CL: watermelon anthrax bacteria: (Colletotrichumlagenarium); FO: cucumber fusarium axysporum (Fusarium oxysporum); GZ: fusarium graminearum (Gibberella zeae); PG: rice blast fungus (Phyricularia grisea (Cooke) Sacc.); PI: phytophthora infestans (Phytophthorainfestans (Mont.) de Bary); PP: ring rot of apple bacterium (Physalospora piricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); RS: dry thread Pyrenomycetes (Rhizoctonia solani kuhn), these bacterial classifications can be represented the kind of most of pathogenic bacteria that the field takes place in the agriculture production.Thalli growth rate method measurement result sees Table 2, table 2 shows, major part of the present invention contains the 4-methyl isophthalic acid, 2, the bishydrazide compound of 3-thiadiazoles group has in various degree restraining effect to the growth of most of pathogenic fungi of measuring, and its bacteriostatic activity is significantly higher than the bacteriostatic activity of positive control medicament worm hydrazides.
Embodiment 81: the 4-methyl isophthalic acid that contains of the present invention, 2, the effect of the derivative induced tobacco resisting tobacco mosaic virus of bishydrazide of 3-thiadiazoles group
The result of the determination test of induced activity shows, the plant inducing anti-disease activator BTH of standard and tiadinil energy evoking tobacco produce the resistance to TMV, major part of the present invention contains the 4-methyl isophthalic acid, 2, the bishydrazide derivative of 3-thiadiazoles group has the activity of the anti-TMV of evoking tobacco preferably, and the induce effect of part of compounds when 100 mcg/ml are irritated 10 milliliters of roots reached 85%.Be because above-claimed cpd has become to have the 4-methyl isophthalic acid of inducing anti-disease cytotoxic activity at the tobacco vivo degradation, 2,3-thiadiazoles-5-formic acid, from chemical structure, C=O in the 5-position all can be by water molecules or OH in plant materials for all compounds of the present invention
-The ion attack, thus hydrolysis goes out the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, consistent with the meta-bolites of TDL.Therefore, compound of the present invention has Antiphytoviral and inducing plant and produces the effect that viral diseases of plants is produced resistance.
Embodiment 82: the 4-methyl isophthalic acid that contains of the present invention, and 2, the bishydrazide derivative of 3-thiadiazoles group and antiviral agent are combined in the application in control agricultural and forestry and the gardening plant virus disease
Contain the 4-methyl isophthalic acid, 2, the bishydrazide derivative of 3-thiadiazoles group and existing Antiphytoviral medicament diazosulfide, tiadinil, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formiate, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, the DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, the first thiophene lures amine or Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, any 1 or the combination of 2 compounds can be used for preventing and treating Agricultural pests such as Asiatic migrotory locust in the allyl isothiazole, clouding car locust, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, the east mole cricket, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian manages thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, green leaf hopper, chlorita biguttula, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, the flat angle of sugarcane plant hopper, cotten aphid, green bugs, grain aphid, black peach aphid, kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, ceroplastes rubens, the hard a red-spotted lizard of Korea's ball, pear lace bug, the banana lace bug, thin corner piece stinkbug, little minute pirate bugs, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, Nezara viridula smaragdula Fabricius., green plant bug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, cnidocampa flavescens walker, brown slug moth, thosea siensis, gelechiid, pink bollworm, brachmia triannuella, small cabbage moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, the apple Spilonota lechriaspis, brown belt length leaf roller, intend smaller apple leaf roller, striped rice borer, bean-pod borer, Pyrausta nubilalis (Hubern)., yellow rice borer, Oeobia undalis, Cnaphalocrocis medinali(rice leaf roller), the bar snout moth's larva, the wild snout moth's larva of lap leaf, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point diamond drill, black cutworm, big cutworm, yellow cutworm, steal poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, the straight burr rice hesperiidae, pelopidas mathias, the oranges and tangerines swallowtail butterfly, Common Mormon, small white, pyrameis indica, the yellow a kind of butterfly harmful to crop plants of ramie, the beans blister beetle, the Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, the little buprestid beetle of oranges and tangerines, gold edge buprestid beetle, tenebrio molitor, dark mealworm, red flour beetle, confused flour beetle, the verdigris different beetle, black dull cockchafer, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, big daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, Phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pear fruit sawfly, the yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm is hanged the cocoon ichneumon wasp, bollworm tooth lip ichneumon wasp, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, the melon trypetid, the latent fly of wheat leaf ash, Americal rice leaf miner, the black fly of diving of beans stalk, frit fly, plant fly, onion fly, the radish fly, full skirt chases after posts fly, Pyrausta nubilalis (Hubern). is strict posts fly, armyworm lacks must post fly etc.; Inducing plant produces the resistance to virus disease and fungal disease simultaneously, the anti-TMV of evoking tobacco or be used for directly preventing and treating TMV can be used for inducing paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, genseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, melon, really, tea, wild vegetable, bamboo shoots, hops, agricultural plantss such as pepper, gardening plant, economic plants, forestry plant produces the control to insect especially infection insect and virus disease.Above-mentionedly contain 1,2, the bishydrazide derivative of 3-thiadiazoles group and the ratio of commodity antiviral agent in composition are 1%: 99% to 99%: 1%, and the formulation of composition processing is selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, can disperse in dense dose, seed treatment emulsion, aqueous emulsion, big granula, granule, microemulsion, oil-suspending agent, finish, the seed with coated pesticidal, suspended emulsion agent, water-soluble granule, soluble thick agent, water-dispersible granules any one; All show summation action or synergism between these compositions, when keeping insecticidal activity, the effect that the effect of its antiviral activity is all used separately greater than any one compound, the result of all mensuration is all greater than 80%; Do not have to find to have the composition of antagonistic action, the drug effect lasting period of composition has all surpassed 21 days.
The staple crop that these compositions are suitable for comprises that cereal crop (comprise paddy, wheat, barley, oat, corn, millet, Chinese sorghum etc.), tuber crops (comprise sweet potato, potato, cassava etc.), legume crop (comprises soybean, broad bean, pea, mung bean, red bean etc.) and fibre crops (cotton, crudefiber crop, silkworm and mulberry etc.), oil crops (peanut, rape, sesame, soybean, Sunflower Receptacle etc.), sugar crop (beet, sugarcane etc.), beverage crops (tealeaves, coffee, cocoa etc.), hobby crop (tobacco leaf etc.), medicinal crop (genseng, the bulb of fritillary etc.), tropical crops (rubber, coconut, oil palm, sisal hemp etc.) food crop and fruit such as, flowers, oil plant, sugar material and cotton, fiber crops, tea, tobacco, cash crop and plantation melons such as Chinese medicinal materials, really, tea, silkworm and mulberry, vegetables (containing various wild vegetable etc.), bamboo shoots, flowers and ornamental plant, hops, medicinal material, pepper, garden crop such as tobacco (flue-cured tobaccos such as seedling and other garden crops, air-curing of tobacco leaves, suncured tabacco), vegetables, (tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic etc.), melon (watermelon, muskmelon, hami melon, pawpaw etc.), beans (soybean, broad bean, pea-pods etc.), potato, wheat, corn, paddy rice, peanut, fruit tree, (apple, banana, citrus, peach, papaya), flowers (as orchid), potted landscape etc.; Virus disease comprises tobacco mosaic virus disease, various melon virus diseases, various solanberry viroid diseases, the beans virus disease, the Cruciferae virus disease, the grain and oil crop virus disease, cotton virus disease and various fruit tree virus diseases etc. wherein endanger serious mainly containing: tobacco virus, peppery pimento virus disease, tomato virus disease, Chinese cabbage virus disease, the paddy rice virus disease comprises rice dwarf virus disease, yellow dwart, stripe virus disease, the fern leaf of tomato viral disease, sick and the tobacco veinal necrosis virus disease of chilli pepper mosaic virus, the corn short mosaic disease, cauliflower mosaic virus, the oranges and tangerines virus disease, cymbidium mosaic virus, cybidium ring spot virus etc.
Embodiment 83: the 4-methyl isophthalic acid that contains of the present invention, 2, the application in the bishydrazide derivative of 3-thiadiazoles group and sterilant combination control agricultural and forestry and the gardening plant disease
Bioassay results shows; Of the present invention all contain the 4-methyl isophthalic acid; 2; The bishydrazide derivative of 3-thiadiazoles group and existing bactericide such as diazosulfide; Tiadinil; Tisocromide; The first thiophene lures amine; The 4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formic acid; The 4-methyl isophthalic acid; 2; 3-thiadiazoles-5-sodium formate; The 4-methyl isophthalic acid; 2,3-thiadiazoles-5-Ethyl formate; The DL-beta-aminobutyric acid; Virazole; Antofine; Ningnanmycin; Tisocromide; The first thiophene lures amine or salicylic acid; Frost urea cyanogen; Thiram; Ziram; Mancozeb; Aliette; Thiophanate-methyl; Bravo; The enemy can be loose; Procymidone; Fenpropidin; Thiophanate methyl; Thiophanate; Metalaxyl-M; Salicylic acid; Flumorph; Dimethomorph; Efficient metalaxyl; Efficient M 9834; Two chlorine zarilamids; Flusulfamide; The first flusulfamide; Thiophene fluorine bacterium amine; Flutolanil; Tecloftalam; Ring propionyl bacterium amine; Cyflufenamid; Fenhexamid; Zarilamid; Silthiopham; Furametpyr; The pyrrole metsulfovax; Mandipropamid; Zoxamide; Fenfuram; Carboxin; Chlozolinate; Iprodione; Fluoxastrobin; Dimoxystrobin; Fluoxastrobin; Kresoxim-methyl; SSF 126; Orysastrobin; ZEN 90160; Pyraclostrobin; Oxime bacterium ester; Enestroburin; Alkene oxime amine; Oxygen ring azoles; Bromuconazole; Cyproconazole; Difenoconazole; Alkene azoles alcohol; Efficient alkene azoles alcohol; Epoxiconazole; RH-7592; Fluquinconazole; Flusilazole; Flutriafol; Own azoles alcohol; Glyoxalin; Plant the bacterium azoles; Metconazole; Nitrile bacterium azoles; Penconazole; Propiconazole; Prothioconazoles; Simeconazoles; Tebuconazole; Tetraconazole; Triadimenol; Triticonazole; Bitertanol; Probenazole; Furidazol; Imazalil; Efficient imazalil; Prochloraz; Fluorine bacterium azoles; Cyazofamid; Fenamidone; The Evil imidazoles; Pefurazoate; Famoxadone; SYP-Z048; Hymexazo; The spirit of Evil frost; Guardian; Grandox fumigant; Octhilinone; Benthiozole; Dodemorph; Butadiene morpholine; Tridemorph; Fenpiclonil; Fludioxonil; Fluazinam; Pyrifenox; Ring pyridine bacterium amine; Boscalid; Fluopicolide; Pyridine bacterium amine; Cyprodinil; The fluorine mepanipyrim; Ferimzone; Mepanipyrim; Phonetic mould amine; Fenarimol; Nuarimol; Chinomethionat; Dithianon; Ethoxyquin; Oxyquinoline; The third oxygen quinoline; Benzene oxygen quinoline; The mould prestige of second; Iprovalicarb; The benzene metsulfovax; Propamocarb; Methasulfocarb; Edifenphos; IBP; Pyrazophos; Tolelofos-methyl; Blasticidin-S; Kasugarnycin; Polyoxin; Polyoxin; Valida; Jinggangmeisu; Streptomysin; Metalaxyl; Furalaxyl; M 9834; Ofurace; Mebenil; Carbendazim; Benomyl; Thiophanate-methyl; Triazolone; Bupirimate; Dimethirimol; The phonetic phenol of second; Difoltan; Captan; Folpet; Vinclozolin; Fluoromide; Dimethachlon; Bravo; Isoprothiolane; Kitazine; Yekuzuo; Pentachloronitrobenzene; Mancozeb; Propineb; Phosethyl-Al; Sulphur; Bordeaux mixture; Copper sulphate; Copper oxychloride; Cuprous oxide; Kocide SD; Metrafenone; Pencycuron; Diclomezin; Rabcide; Pyroquilon; Volution bacterium amine; Tricyclazole; Triforine; The pyridine of many fruits; The hot salt of biguanides; Iminoctadine; Botran; The benzene flusulfamide; The toluene flusulfamide; K-281; Fenaminosulf; Oxolinic acide; Probenazole; Bronopol; Iodomethane; Metham-sodium; Enemy's line ester; Dazomet; Nemamort; Lythidathion; Cadusafos; Fensulfothion; Thionazin; Fenamiphos; Phonamiphos; Dichlofenthion; Isazofos; Fosthietan; Oxamyl; Aldicarb; Carbofuran; Vikane; Dichloropropylene; Dichloro-isonicotinic acid; Other known any any one or two kinds that can be used as in the bactericide such as allyl isothiazole are used in combination; The 4-methyl isophthalic acid that contains of the present invention, 2, the mass ratio of bishydrazide derivative in composition of 3-thiadiazoles group is 1%-90%, and the prevention effect of medicament is good, these compositions have certain synergism and summation action, do not find to have the composition of antagonistic action; Above-mentioned composition can be used for the control of agricultural plants disease and gardening plant disease, controlling object comprises the Achyla of Oomycete, Aphanomyces, pythium, phytophthora, Sclerospora, Plasmopara, false Peronospora, the pathogen or the virus that belong to cause kind of food crop surplus the Peronosporas etc. 20, cash crop, gardening plant and forestry plant produce pyorrhea, black powder, white powder, the rust powder, continuous mould, downy mildew, scab, leaf roll, tumour, purple plague purpura, leaf burns, leaf is withered, wilt, the wheel line, gummosis, ulcer, the angle spot, Huang withers, floral leaf, foxiness, rot, perforation, fallen leaves, shedding, the disease of symptoms such as cladoptosis, above-mentionedly contain 1,2, the bishydrazide derivative of 3-thiadiazoles group and the ratio of commodity sterilant in composition are 1%:99% to 99%:1%, and the formulation of composition processing is selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, can disperse dense dose, seed treatment emulsion, aqueous emulsion, big granula, granule, microemulsion, oil-suspending agent, finish, seed with coated pesticidal, suspended emulsion agent, water-soluble granule, soluble thick agent, in the water-dispersible granules any one.
Utilize similar method to determine, the 4-methyl isophthalic acid that contains of the present invention, 2, the combination between the bishydrazide compound of 3-thiadiazoles group and the above-mentioned commodity sterilant can be used for the disease of inducing disease-resistant indigenous bacteria of agricultural crops and forestry plant and gardening plant and plant pathogenic fungi to cause.These crops comprise: cereal crop (comprise paddy, wheat, barley, oat, corn, millet, Chinese sorghum etc.), tuber crops (comprise sweet potato, potato, cassava etc.), legume crop (comprises soybean, broad bean, pea, mung bean, red bean etc.) fibre crops (cotton, crudefiber crop, silkworm and mulberry etc.), oil crops (peanut, rape, sesame, soybean, Sunflower Receptacle etc.), sugar crop (beet, sugarcane etc.), beverage crops (tealeaves, coffee, cocoa etc.), hobby crop (tobacco leaf etc.), medicinal crop (genseng, the bulb of fritillary etc.), tropical crops (rubber, coconut, oil palm, sisal hemp etc.) food crop and fruit such as, flowers, oil plant, sugar material and cotton, fiber crops, tea, tobacco, cash crop and plantation melons such as Chinese medicinal materials, really, tea, silkworm and mulberry, vegetables (containing various wild vegetable etc.), bamboo shoots, flowers and ornamental plant, hops, medicinal material, pepper, garden crops such as seedling and other garden crops.
Embodiment 84: the 4-methyl isophthalic acid that contains of the present invention, 2, the application in the bishydrazide derivative of 3-thiadiazoles group and sterilant combination control agricultural and forestry and the gardening plant insect pest
Of the present invention all contain the 4-methyl isophthalic acid, 2, the bishydrazide derivative of 3-thiadiazoles group and the mass ratio of commodity insecticides are classified 1%: 99% to 99%: 1% as, spray after can directly converting water, comprise agricultural in its preparation and go up acceptable solvent and emulsifying agent and solubility promoter and synergistic agent etc., the formulation of composition processing is selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, can disperse dense dose, seed treatment emulsion, aqueous emulsion, big granula, granule, microemulsion, oil-suspending agent, finish, seed with coated pesticidal, suspended emulsion agent, water-soluble granule, soluble thick agent, in the water-dispersible granules any one; The insect pest that can prevent and treat mainly contains red spider, Asiatic migrotory locust, clouding car locust, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, the east mole cricket, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian manages thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, green leaf hopper, chlorita biguttula, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, the flat angle of sugarcane plant hopper, cotten aphid, green bugs, grain aphid, black peach aphid, kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, ceroplastes rubens, the hard a red-spotted lizard of Korea's ball, pear lace bug, the banana lace bug, thin corner piece stinkbug, little minute pirate bugs, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, Nezara viridula smaragdula Fabricius., green plant bug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, cnidocampa flavescens walker, brown slug moth, thosea siensis, gelechiid, pink bollworm, brachmia triannuella, small cabbage moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, the apple Spilonota lechriaspis, brown belt length leaf roller, intend smaller apple leaf roller, striped rice borer, bean-pod borer, Pyrausta nubilalis (Hubern)., yellow rice borer, Oeobia undalis, Cnaphalocrocis medinali(rice leaf roller), the bar snout moth's larva, the wild snout moth's larva of lap leaf, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point diamond drill, black cutworm, big cutworm, yellow cutworm, steal poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, the straight burr rice hesperiidae, pelopidas mathias, the oranges and tangerines swallowtail butterfly, Common Mormon, small white, pyrameis indica, the yellow a kind of butterfly harmful to crop plants of ramie, the beans blister beetle, the Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, the little buprestid beetle of oranges and tangerines, gold edge buprestid beetle, tenebrio molitor, dark mealworm, red flour beetle, confused flour beetle, the verdigris different beetle, black dull cockchafer, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, big daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, Phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pear fruit sawfly, the yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm is hanged the cocoon ichneumon wasp, bollworm tooth lip ichneumon wasp, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, the melon trypetid, the latent fly of wheat leaf ash, Americal rice leaf miner, the black fly of diving of beans stalk, frit fly, plant fly, onion fly, the radish fly, full skirt chases after posts fly, Pyrausta nubilalis (Hubern). is strict posts fly, armyworm lacks Agricultural pests such as must posting fly, forestry pest, gardening pest insect and sanitary insect pest, controlling mode also comprises double controlling simultaneously; The 4-methyl isophthalic acid that contains of the present invention, 2, the bishydrazide compound of 3-thiadiazoles group can with the sterilant of following group in one or more mix use: Chlorpyrifos 94, the inferior Nong in ground, acetamiprid, Affirm (Merck Co.), more visit rhzomorph, Avrmectin, pleocidin, fenvalerate, efficient fenvalerate, Cypermethrin, effective cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, the Beta-cyfloxylate, cyfloxylate, the Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, cyhalothrin, bifenthrin, permethrin, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, acetamiprid, Ti304, imidaclothiz, thiophene worm quinoline, thiophene worm piperazine, thiophene worm amine, MTI-446, clothianadin, Da Tenan, diflubenzuron, young urea goes out, Teflubenzuron, deinsectization is grand, fluorine bell urea, flufenoxuron, the pyridine worm is grand, the Acarus tritici urea, the poisonous insect urea, penfluron, Noviflumuron, flucycloxuron, Novaluron, fluorine pyridine urea, Bay sir 6874, piperazine worm urea, Bistrifluron, furans worm hydrazides, the worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides, Rogor, omethoate, SD-1750, acephate, triazophos, Resitox, pyridaphenthione, isazofos, Ro 7-5050, SevinCarbaryl, Aphox, meta-tolyl-N-methylcarbamate (MTMC), isoprocarb, cartap, fenobucarb, leaf disperses, carbaryl, benfuracarb, carbosulfan, cartap, bromopropylate, hexythiazox, azoles mite ester, pyridaben, four mite piperazines, alkynes mite spy, the butyl ether urea, benfuracarb, pyrrole aphid ketone, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, Buprofezin, ethoprophos, fluorine worm nitrile, the desinsection list, disosultap, Flubendiamide, chlorine insect amide or tebufenpyrad, bromothalonil, pyrazine ketone, second mite azoles, tebufenpyrad, the young ketone of rattling away, the pyrrole propyl ether, emaricin etc., the preventive effect of combination medicament is good, and drug effect is played stably.
Embodiment 85: the 4-methyl isophthalic acid that contains of the present invention, 2, the bishydrazide derivative of 3-thiadiazoles group and the complete processing and the stability of commercially available agricultural chemical compound preparation
The 4-methyl isophthalic acid that contains of the present invention, 2, the bishydrazide derivative of 3-thiadiazoles group and the mixed preparation complete processing of commercially available agricultural chemical see Table 3, table 3 as seen, most medicament all can be processed according to the method for statement, the main component of liquid preparation is effective constituent and solubility promoter and tensio-active agent and synergistic agent, antifreezing agent, stablizer, other component etc. such as thickening material or permeate agent, the composition of solid preparation mainly includes the effect composition, other agriculturals such as tensio-active agent and filler go up the acceptable adjuvant component, preparation to processing carries out cold storage test, liquid preparation is placed 1 week not have to precipitate at 0 ± 2 degree centigrade and is separated out, solid preparation placed for 2 weeks at 54 ± 2 degrees centigrade, caking phenomenon does not appear in medicament, the medicament drug effect that all preparations store before and after placing does not have significant difference, the rate of decomposition of mixing effective constituent illustrates the medicament qualified stability in 5%.
Table 1 synthetic of the present invention contains the 4-methyl isophthalic acid, and 2, the chemical structure of the bishydrazide derivative of 3-thiadiazoles group
Table 1 synthetic of the present invention contains the 4-methyl isophthalic acid, and 2, the chemical structure (continuing) of the bishydrazide derivative of 3-thiadiazoles group
Table 1 synthetic of the present invention contains the 4-methyl isophthalic acid, and 2, the chemical structure (continuing) of the bishydrazide derivative of 3-thiadiazoles group
The biological activity determination result (%) of the compound among table 3 the present invention
| Numbering | Test code number | AS? | CA? | GZ? | PP? | BC? | RC? | PS? | SS? | PI? | PXL2? | PXL4? | ?M2? |
| I-1? | YZK-6-32? | 43.48? | 58.33? | 18.75? | 17.50? | 63.16? | 56.67? | 41.03? | 91.49? | 86.96? | 0? | -? | ?100? |
| I-2? | YZK-6-40? | 47.83? | 52.78? | 33.33? | 25.00? | 47.37? | 60.00? | 17.95? | 100.00? | 34.78? | 7.70? | -? | ?20? |
| I-3? | YZK-6-42? | 39.13? | 52.78? | 29.17? | 20.00? | 21.05? | 63.33? | 26.92? | 100.00? | 26.09? | 0? | -? | ?20? |
| I-4? | YZK-6-45? | 34.78? | 50.00? | 31.25? | 30.00? | 5.26? | 53.33? | 32.05? | 97.87? | 13.04? | 14.60? | -? | ?10? |
| I-5? | YZK-7-42? | 16.67? | 14.29? | 20.45? | 50.00? | 17.39? | 30.61? | 1.18? | 79.17? | 14.29? | -? | 30.00? | ?10? |
| I-6? | ZQX-2-18? | 23.81? | 21.05? | 32.50? | 52.00? | 60.00? | 63.16? | 49.02? | 34.21? | 37.50? | 36.84? | -? | ?20? |
| I-7? | YZK-6-41? | 43.48? | 58.33? | 33.33? | 15.00? | 21.05? | 58.33? | 34.62? | 95.74? | 26.09? | 25.00? | -? | ?10? |
| I-8? | YZK-7-35? | 22.22? | 21.43? | 22.73? | 8.00? | 30.43? | 20.41? | 0? | 50.00? | 42.86? | 78.90? | -? | ?10? |
| I-9? | YZK-7-38? | 27.78? | 7.14? | 20.45? | 40.00? | 26.09? | 32.65? | 2.35? | 58.33? | 28.57? | 0.0? | -? | ?30? |
| I-10 * | YZK-7-45? | 33.33? | 21.43? | 22.73? | 34.00? | 52.17? | 36.73? | 29.41? | 29.17? | 38.10? | 25.00? | -? | ?100? |
| I-11? | YZK-7-15? | 50.00? | 14.29? | 70.00? | 28.57? | 38.30? | 53.97? | 28.92? | 36.67? | 32.00? | 17.10? | -? | ?10? |
| I-12? | YZK-7-19-5? | 36.36? | 4.76? | 72.00? | 40.00? | 57.45? | 47.62? | 19.28? | 43.33? | 44.00? | 26.30? | -? | ?10? |
| I-13? | YZK-6-37? | 30.43? | 55.56? | 33.33? | 62.50? | 42.11? | 58.33? | 17.95? | 97.87? | 26.09? | 2.40? | -? | ?10? |
| I-14? | WH-2-34? | 33.33? | 36.84? | 22.50? | 44.00? | 56.00? | 47.37? | 47.06? | 30.26? | 58.33? | 15.00? | -? | ?10? |
| I-15? | WH-2-35? | 28.57? | 52.63? | 15.00? | 34.00? | 20.00? | 84.21? | 37.25? | 30.26? | 54.17? | 45.90? | -? | ?40? |
| I-16? | WH-3-18? | 33.33? | 31.58? | 15.00? | 44.00? | 68.00? | 52.63? | 33.33? | 26.32? | 62.50? | 5.00? | -? | ?30? |
| I-17? | YZK-7-50-1? | 38.89? | 28.57? | 27.27? | 52.00? | 60.87? | 40.82? | 0? | 54.17? | 52.38? | -? | 45.00? | ?10? |
| I-18? | YZK-7-48? | 39.13? | 50.00? | 31.25? | 72.50? | 63.16? | 65.00? | 23.08? | 100.00? | 69.57? | -? | 22.50? | ?30? |
| I-19? | WH-2-33? | 42.86? | 26.32? | 37.50? | 58.00? | 60.00? | 60.53? | 37.25? | 34.21? | 37.50? | 5.00? | -? | ?10? |
| I-20? | YZK-7-11? | 16.67? | 28.57? | 20.45? | 24.00? | 47.83? | 48.98? | 36.47? | 47.92? | 4.76? | 69.70? | -? | ?10? |
| I-21? | YZK-6-36? | 39.13? | 58.33? | 29.17? | 15.00? | 31.58? | 63.33? | 3.85? | 97.87? | 26.09? | 33.30? | -? | ?20? |
| I-22? | YZK-6-39? | 34.78? | 58.33? | 27.08? | 40.00? | 31.58? | 63.33? | 47.44? | 100.00? | 21.74? | 14.30? | -? | ?40? |
| I-23? | YZK-7-3? | 45.45? | 16.67? | 70.00? | 37.14? | 40.43? | 39.68? | 56.63? | 26.67? | 12.00? | -? | 84.62? | ?30? |
| I-24? | YZK-7-6? | 50.00? | 35.71? | 36.36? | 4.00? | 69.57? | 61.22? | 47.06? | 93.75? | 28.57? | 55.6? | -? | ?20? |
| I-25? | YZK-7-16? | 42.86? | 0? | 0? | 58.97? | 18.18? | 54.84? | 36.62? | 36.36? | 9.52? | 50.00? | -? | ?20? |
| I-26? | YZK-7-17? | 54.55? | 28.57? | 84.00? | 50.00? | 51.06? | 71.43? | 32.53? | 16.67? | 48.00? | 42.50? | -? | ?0? |
| I-27? | WH-5-28? | 0? | 0? | 7.69? | 18.42? | 37.93? | 13.16? | 7.04? | 44.19? | 2.00? | ? | 22.50? | ?20? |
| I-28? | WH-2-32? | 52.38? | 36.84? | 25.00? | 38.00? | 40.00? | 47.37? | 50.98? | 32.89? | 41.67? | 0? | -? | ?-? |
| I-31? | WH-3-15? | 15.00? | 17.65? | 28.89? | 34.85? | 50.00? | 30.00? | 25.00? | 28.95? | 22.22? | 5.26? | ? | ?60? |
| I-32? | WH-3-21? | 42.86? | 57.89? | 30.00? | 66.00? | 60.00? | 68.42? | 66.67? | 40.79? | 45.83? | 17.07? | ? | ?10? |
| I-33? | WH-3-25? | 33.33? | 47.37? | 25.00? | 54.00? | 60.00? | 39.47? | 35.29? | 26.32? | 54.17? | 10.00? | ? | ?30? |
| I-34? | WH-4-18? | 5.26? | 0? | 0? | 18.42? | 34.48? | 0? | 0? | 16.28? | 22.22? | -? | 48.78? | ?20? |
| I-35? | WH-4-30? | 0? | 0? | 25.00? | 26.67? | 41.18? | 84.00? | 40.82? | 30.26? | 8.33? | -? | 35.00? | ?20? |
| I-36? | WH-4-37? | 26.67? | 22.22? | 29.17? | 23.33? | 55.88? | 24.00? | 63.27? | 34.21? | 25.00? | -? | 44.12? | ?10? |
| I-37? | WH-5-11? | 0? | 0? | 11.54? | 21.05? | 20.69? | 18.42? | 0? | 20.93? | 3.70? | -? | 12.95? | ?0? |
| I-38? | WSX-44? | 22.22? | 63.64? | 24.39? | 28.13? | 32? | 41.67? | 28.95? | 16.67? | 16.67? | 12.50? | ? | ?40? |
| I-39? | WH-4-40? | 5.26? | 0? | 0? | 5.26? | 3.1? | 10.53? | 0? | 62.79? | 3.70? | -? | 24.39? | ?10? |
| II-2? | YZK-7-29? | 33.33? | 21.43? | 31.82? | 28.00? | 34.78? | 28.57? | 3.53? | 93.75? | 28.57? | 67.50? | -? | ?100? |
| II-3? | WH-4-6? | 0? | 66.67? | 16.67? | 33.33? | 55.88? | 14.00? | 48.98? | 31.58? | 4.17? | 12.20? | -? | ?20? |
| II-4? | YZK-6-48? | 34.78? | 58.33? | 27.08? | 22.50? | 26.32? | 55.00? | 29.49? | 95.74? | 0? | 37.00? | -? | ?0? |
| II-5? | YZK-7-44? | 27.78? | 21.43? | 22.73? | 70.00? | 34.78? | 2.04? | 2.35? | 58.33? | 33.33? | 28.95? | -? | ?10? |
| II-6? | ZQX-2-20-b? | 33.33? | 21.05? | 25.00? | 52.00? | 60.00? | 34.21? | 45.10? | 28.95? | 33.33? | -? | 10.00? | ?10? |
| II-7? | WH-4-7? | 26.67? | 33.33? | 41.67? | 33.33? | 26.47? | 18.00? | 59.18? | 23.68? | 20.83? | -? | 27.50? | ?10? |
| II-8? | YZK-7-34? | 27.78? | 14.29? | 27.27? | 32.00? | 30.43? | 40.82? | 15.29? | 81.25? | 0? | 23.70? | -? | ?20? |
| II-9? | YZK-7-39? | 38.89? | 35.71? | 20.45? | 36.00? | 56.52? | 36.73? | 29.41? | 58.33? | 14.29? | 25.00? | -? | ?0? |
| II-10? | YZK-7-46? | 50.00? | 42.86? | 31.82? | 32.00? | 13.04? | 48.98? | 10.59? | 68.75? | 23.81? | -? | 42.50? | ?20? |
| II-11? | YZK-7-19-1? | 40.91? | 26.19? | 76.00? | 34.29? | 31.91? | 61.90? | 15.66? | 53.33? | 44.00? | 2.40? | -? | ?30? |
| II-12? | YZK-7-31? | 44.44? | 42.86? | 25.00? | 26.00? | 13.04? | 28.57? | 5.88? | 47.92? | 14.29? | 96.60? | -? | ?10? |
| II-13? | WH-3-43-B? | 20.00? | 11.76? | 2.22? | 27.27? | 33.33? | 40.00? | 37.50? | 27.63? | 29.63? | 2.86? | ? | ?40? |
| II-14? | WH-3-32? | 5.26? | 0? | 2.50? | 26.32? | 24.14? | 18.42? | 0? | 62.79? | 3.70? | ND? | 35.00? | ?ND? |
| II-15? | WH-3-33? | 52.38? | 31.58? | 22.50? | 40.00? | 48.00? | 63.16? | 33.33? | 35.53? | 41.67? | 32.40? | -? | ?100? |
| II-16? | WH-3-22? | 52.38? | 42.11? | 30.00? | 54.00? | 76.00? | 60.53? | 45.10? | 32.89? | 66.67? | 13.33? | -? | ?40? |
| II-17? | WH-4-12? | 22.22? | 27.27? | 46.34? | 21.88? | 28.00? | 22.22? | 21.05? | 100? | 8.33? | 15.80? | -? | ?20? |
The biological activity determination result (%) (continuing) of the compound among table 3 the present invention
| Numbering | Test code number | AS? | CA? | GZ? | PP? | BC? | RC? | PS? | SS? | PI? | PXL2? | PXL4? | ?M2? |
| II-18? | YZK-7-49? | 44.44? | 50.00? | 20.45? | 32.00? | 30.43? | 46.94? | 24.71? | 68.75? | 14.29? | 34.21? | -? | ?10? |
| II-19? | YZK-6-50? | 47.83? | 52.78? | 39.58? | 5.00? | 31.58? | 70.00? | 17.95? | 97.87? | 21.74? | 33.30? | -? | ?30? |
| II-20? | YZK-7-33? | 38.89? | 35.71? | 34.09? | 36.00? | 60.87? | 44.90? | 10.59? | 95.83? | 19.05? | 0? | -? | ?100? |
| II-23? | YZK-7-4? | 33.33? | 28.57? | 31.82? | 68.00? | 60.87? | 36.73? | 1.18? | 81.25? | 28.57? | 12.10? | -? | ?10? |
| II-25? | WH-3-10? | 28.57? | 26.32? | 30.00? | 42.00? | 72.00? | 50.00? | 52.94? | 32.89? | 45.83? | 7.50? | ? | ?40? |
| II-26? | WH-3-14? | 28.57? | 31.58? | 22.50? | 58.00? | 44.00? | 50.00? | 74.51? | 43.42? | 58.33? | 2.80? | ? | ?30? |
| II-27? | WSX-54? | 44.44? | 42.86? | 22.73? | 0? | 17.39? | 53.06? | 8.24? | 68.75? | 33.33? | 6.20? | -? | ?30? |
| II-28? | WH-3-42? | 33.33? | 26.32? | 37.50? | 30.00? | 64.00? | 34.21? | 49.02? | 43.42? | 29.17? | 4.88? | ? | ?40? |
| II-29? | WH-2-39? | 47.62? | 36.84? | 22.50? | 54.00? | 56.00? | 50.00? | 45.10? | 38.16? | 50.00? | 28.57? | -? | ?0? |
| II-30? | WH-2-44? | 47.62? | 52.63? | 35.00? | 40.00? | 48.00? | 52.63? | 66.67? | 34.21? | 37.50? | 2.70? | -? | ?20? |
| II-31? | WH-4-14? | 20.00? | 77.78? | 25.00? | 33.33? | 55.88? | 26.00? | 46.94? | 28.95? | 16.67? | 7.69? | ? | ?50? |
| II-32? | WH-3-23? | 42.86? | 21.05? | 37.50? | 42.00? | 36.00? | 81.58? | 29.41? | 31.58? | 41.67? | 5.13? | ? | ?20? |
| II-33? | WH-3-27? | 61.90? | 42.11? | 22.50? | 50.00? | 52.00? | 63.16? | 45.10? | 34.21? | 25.00? | 5.13? | ? | ?10? |
| II-36? | WH-4-42? | 13.33? | 33.33? | 54.17? | 36.67? | 41.18? | 14.00? | 55.10? | 31.58? | 20.83? | -? | 34.15? | ?30? |
| II-38? | WSX-50? | 27.78? | 36.36? | 12.20? | 37.50? | 28.00? | 41.67? | 23.68? | 41.67? | 16.67? | 15.80? | ? | ?20? |
| III-1? | WH-2-36? | 42.86? | 26.32? | 37.50? | 58.00? | 60.00? | 68.42? | 70.59? | 23.68? | 41.67? | 15.00? | -? | ?30? |
| III-2? | WH-2-43? | 10.00? | 11.76? | 13.33? | 27.27? | 66.67? | 20.00? | 28.13? | 23.68? | 25.93? | 10.00? | -? | ?10? |
| IV-1? | ZQX-2-20-a? | 38.10? | 31.58? | 35.00? | 44.00? | 72.00? | 52.63? | 21.57? | 31.58? | 54.17? | -? | 25.00? | ?10? |
| IV-2? | WH-3-43-A? | 10.00? | 0? | 0? | 31.82? | 33.33? | 60.00? | 43.75? | 32.89? | 14.81? | ? | 27.5? | ?10? |
| V-1? | WH-5-16? | 15.79? | 0? | 0? | 31.58? | 44.83? | 15.79? | 0? | 44.19? | 0? | ? | 34.46? | ?10? |
| VI-1? | WSX-40? | 11.11? | 54.55? | 12.20? | 18.75? | 20.00? | 44.44? | 23.68? | 20.83? | 12.50? | 0? | 28.57? | ?10? |
| CXJ ** | The worm hydrazides | 5.26? | 0? | 4.76? | 9.52? | 11.76? | 14.00? | 2.50? | 1.18? | 4.17? | 10.00? | 20.00? | ?40? |
*: mosquito larvae 1 μ g/mL is 100%; 0.5 μ g/mL is 10%;
*: the worm hydrazides;
PXL2: small cabbage moth (Plutella xylostella L.) 200 μ g/mL; PXL4: small cabbage moth (Plutella xylostella L.) 400 μ g/mL; M2: mosquito larvae: 2 μ g/mL.
Table 3 contains the 4-methyl isophthalic acid, and 2, the bishydrazide derivative of 3-thiadiazoles group mixes the working method of using preparation with conventional pesticide
| Liquid preparation is formed | Content (%) | Solid preparation is formed | Content (%) | Explanation |
| Other agricultural chemicals of Compound I or II or III or IV+ | ?1-90? | Other agricultural chemicals of Compound I or II or III or IV+ | 1-90? | The principle of combination is to examine synergy or consider doublely to control and lighten one's labor and save the dispenser cost |
| Solubility promoter | ?2-8? | Sodium lauryl sulphate | 1-5? | -? |
| Tensio-active agent | ?2-10? | Diatomite | 5-30? | -? |
| Antifreezing agent | ?2-5? | Sodium lignosulfonate | 2-8? | -? |
| Synergistic agent | ?2-8? | Other agriculturals go up the acceptable auxiliary agent | 1-5? | -? |
| Other agriculturals go up acceptable auxiliary agents as, stablizer, thickening material or permeate agent etc. | ?1-5? | Kaolin | Supply 100% | -? |
| Toluene (water) | Supply 100% | ? | ? | ? |
Claims (10)
1. one kind contains 2, and the bishydrazide derivative of 3-thiadiazoles group is characterized in that: have the chemical structure of general formula shown in I, II, III, IV, V, VI:
Wherein: R
1, R
2, R
3, R
4, R
5Be respectively and be selected from phenyl, the 2-aminomethyl phenyl, the 3-aminomethyl phenyl, the 4-aminomethyl phenyl, the 2-p-methoxy-phenyl, the 3-p-methoxy-phenyl, the 4-p-methoxy-phenyl, the 2-chloro-phenyl-, the 3-chloro-phenyl-, the 4-chloro-phenyl-, the 2-fluorophenyl, the 3-fluorophenyl, the 4-fluorophenyl, the 2-trifluoromethyl, the 3-trifluoromethyl, the 4-trifluoromethyl, the 2-nitrophenyl, the 3-nitrophenyl, the 4-nitrophenyl, the 4-ethylphenyl, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-base, the 2-furyl, 2-methyl-2-(4-chloro-phenyl-)-1-propyl group, trichloromethyl, the chrysanthemum acyl group, dichloro chrysanthemum acyl group, 4-fluorobenzene ethyl, 2, the 6-dichlorophenyl, methyl, propyl group, heptyl, 3, the 5-dichlorophenyl, 3, the 5-dimethyl, 3-(2-chloro-phenyl-)-5-methyl-isoxazole-4-base, 2,4-dimethyl-1-phenylpyrazole-3-base, cyclohexyl, 2-fluorobenzene ethyl, 3,6-dichloropyridine-2-base, 5-ethyl-1-methylpyrazole-3-base, the group of 2-fluorobenzene ethyl; Q is arylidene or inferior fatty group.
2. claim 1 is described contains 1,2, the synthetic method of the bishydrazide derivative of 3-thiadiazoles group, and concrete steps are as follows:
A. the preparation of substituted formyl chlorine:
The replacement formic acid that adds 2 mmoles in 50 milliliters of round-bottomed flasks adds the sulfur oxychloride of 12 mmoles again, with reaction mixture with oil bath reflux 3-4 hour, air distillation remove behind the intact sulfur oxychloride of unreacted substituted formyl chlorine, sealing is preserved standby; The amount of substituted formyl chlorine preparation enlarges by corresponding proportion or dwindles;
The preparation of B.N-(substituted formacyl)-N '-tertiary butyl hydrazine:
In 100 milliliters of round-bottomed flasks, add 15 mmole tertiary butyl hydrazonium salt hydrochlorates, add 40 milliliters of methylene dichloride and 5 ml waters and 30 mmole sodium hydroxide again, under induction stirring and ice bath cooling, slowly drip 20 milliliters of dichloromethane solutions of 15 mmole substituted formyl chlorine, dropwise the back room temperature reaction 3 hours, the stopped reaction afterreaction mixes nothing and washes with water, tell organic layer, behind the anhydrous magnesium sulfate drying, rotary evaporation remove desolvate N-(substituted formacyl)-N '-tertiary butyl hydrazine, product need not to be further purified the reaction that is directly used in next step; The amount of N-substituted formacyl-N '-tertiary butyl hydrazine preparation enlarges by corresponding proportion or dwindles;
C.4-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-5-formyl chloride:
4-methyl isophthalic acid with 0.067 mole, 2,3-thiadiazoles-5-formic acid and 29 milliliters of thionyl chlorides join in 100 milliliters of three mouthfuls of round-bottomed flasks, 80 degrees centigrade of following reflux 6 hours, remove excessive thionyl chloride under reduced pressure, underpressure distillation is collected 94-96 degree centigrade cut and is got faint yellow product 9.25 grams under 2000Pa, yield 85%, intermediate 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl chloride sealing is kept in the moisture eliminator standby, the 4-methyl isophthalic acid, 2, the amount of 3-thiadiazoles-5-formyl chloride preparation enlarges by corresponding proportion or dwindles;
The preparation of D.N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine:
In 1000 milliliters of round-bottomed flasks, add 0.4 mole of tertiary butyl hydrazonium salt hydrochlorate, add 450 milliliters of methylene dichloride and 100 ml waters and 0.6 molar sodium hydroxide again, under induction stirring and ice bath cooling, slowly drip 0.4 mole of 4-methyl isophthalic acid, 2,50 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride, dropwise the back room temperature reaction 5 hours, the stopped reaction afterreaction mixes nothing and washes with water, tell organic layer, behind the anhydrous magnesium sulfate drying, removal of solvent under reduced pressure gets N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-and N '-tertiary butyl hydrazine, product need not to be further purified the reaction that is directly used in next step; The amount of N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine preparation enlarges by corresponding proportion or dwindles;
The preparation of E.N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-the formyl radical)-N '-tertiary butyl-N '-substituted formyl hydrazine class compound I:
Get 0.1 mmole N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, join in 50 milliliters of round-bottomed flasks, add acid binding agent 0.12 mmole triethylamine then, the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.1 mmole substituted formyl chlorine down; Dropwise the back and continued stirring reaction 4 hours in room temperature; after reaction finishes; the reaction mixture water is given a baby a bath on the third day after its birth inferior; anhydrous magnesium sulfate drying spends the night; filter the back removal of solvent under reduced pressure, crude product gets N-(4-methyl isophthalic acid, 2 with Virahol or re-crystallizing in ethyl acetate; 3-thiadiazoles-5-formyl radical)-the N '-tertiary butyl-N '-substituted formyl hydrazine class compound I, measure fusing point and
1H NMR determines its chemical structure, and the amount of Compound I preparation enlarges by corresponding proportion or dwindles;
The preparation of F.N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-the formyl radical)-N-tertiary butyl-N '-substituted formyl hydrazine class compound II:
Getting 0.1 mmole N-substituted formacyl-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride, join then in 50 milliliters of round-bottomed flasks, add acid binding agent 0.12 mmole triethylamine, the ice bath cooling slowly drips 0.1 mmole 4-methyl isophthalic acid down, 2,5 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride; Dropwise the back and continued stirring reaction 4 hours in room temperature; after reaction finishes; the reaction mixture water is given a baby a bath on the third day after its birth inferior; anhydrous magnesium sulfate drying spends the night; filter the back removal of solvent under reduced pressure, crude product gets N-(4-methyl isophthalic acid, 2 with Virahol or re-crystallizing in ethyl acetate; 3-thiadiazoles-5-formyl radical)-the N-tertiary butyl-N '-substituted formyl hydrazine class compound II, measure fusing point and
1HNMR determines its chemical structure, and the amount of Compound I I preparation enlarges by corresponding proportion or dwindles;
G.N '-the tertiary butyl-N '-substituted formacyl-N-substituted formacyl-N-4-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-5-formyl hydrazine derivative III:
In 100 milliliters of round-bottomed flasks, add 0.1 mmole N '-tertiary butyl-4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl hydrazine, 0.2 the triethylamine of mmole, 20 milliliters of methylene dichloride stirring and dissolving slowly drip 10 milliliters of dichloromethane solutions that are dissolved with 0.1 mmole substituted formyl chlorine then under condition of ice bath, dropwised in 1 hour, naturally heat up stirring at room 5 hours, saturated NaHCO
3Solution washing, anhydrous Na
2SO
4Dry; filter; the decompression precipitation; (eluent is 60-90 degree centigrade a sherwood oil: ethyl acetate volume ratio 3: 1) get the product N '-tertiary butyl-N '-substituted formacyl-N-substituted formacyl-N-4-methyl isophthalic acid with 200-300 order silica gel column chromatography; 2; 3-thiadiazoles-5-formyl hydrazine derivative III, measure fusing point and
1H NMR determines its chemical structure, and the amount of compound III preparation enlarges by corresponding proportion or dwindles;
H.N '-the tertiary butyl-N-substituted formacyl-N-4-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-5-formyl hydrazine derivative I V:
Adding 0.1 mmole N-substituted formacyl-N '-tertiary butyl hydrazine in 100 milliliters of round-bottomed flasks is dissolved in 20 milliliters of methylene dichloride; add acid binding agent 0.12 mmole triethylamine then; the ice bath cooling slowly drips 0.1 mmole 4-methyl isophthalic acid down; 2; 20 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride; dropwised in 1 hour; naturally heat up; continued stirring reaction 4 hours in room temperature; after reaction finishes; filter the back removal of solvent under reduced pressure; (eluent is 60-90 degree centigrade a sherwood oil to crude product: ethyl acetate volume ratio 3: 1) get N '-tertiary butyl-N-substituted formacyl-N-4-methyl isophthalic acid with 200-300 order silica gel column chromatography; 2,3-thiadiazoles-5-formyl hydrazine derivative I V, measure fusing point and
1H NMR determines its chemical structure, and the amount of compound IV preparation enlarges by corresponding proportion or dwindles;
I.N '-the tertiary butyl-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N-substituted formacyl-N-4-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-5-formyl hydrazine derivative V
Adding 4.54 mmole N-substituted formacyl-N '-tertiary butyl hydrazines in 100 milliliters of round-bottomed flasks is dissolved in 20 milliliters of methylene dichloride; add acid binding agent 6.8 mmole triethylamines then; the ice bath cooling slowly drips 6.8 mmole 4-methyl isophthalic acids down; 2; 20 milliliters of dichloromethane solutions of 3-thiadiazoles-5-formyl chloride; dropwised in 1 hour; naturally heat up; continued stirring reaction 4 hours in room temperature; after reaction finishes; the reaction mixture water is given a baby a bath on the third day after its birth inferior, and anhydrous sodium sulfate drying 60-90 degree centigrade sherwood oil: methylene dichloride mixed solvent recrystallization gets the N '-tertiary butyl-N '-(4-methyl isophthalic acid, 2; 3-thiadiazoles-5-formyl radical)-N-substituted formacyl-N-4-methyl isophthalic acid; 2,3-thiadiazoles-5-formyl hydrazine derivative V, carry out fusing point and
1The mensuration of HNMR is determined its chemical structure, and the amount of compound V preparation enlarges by corresponding proportion or dwindles;
J. the preparation of two-[(N '-tertiary butyl-N '-substituted formacyl)-N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl hydrazine)] derivative VI
In 100 milliliters of round-bottomed flasks, add 7 mmole N '-tertiary butyl-4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formyl hydrazine; the triethylamine of 8 mmoles; 20 milliliters of methylene dichloride stirring and dissolving; under condition of ice bath, slowly drip then and be dissolved with 3.5 mmoles, dropwise, naturally intensification 5 milliliters of the dichloromethane solutions of substituted dimethyl acyl chlorides; stirring at room 4 hours; the reaction mixture water is given a baby a bath on the third day after its birth inferior, anhydrous sodium sulfate drying, removal of solvent under reduced pressure behind the suction filtration; that sherwood oil and methylene dichloride recrystallization get product is two-[(N '-tertiary butyl-N '-substituted formacyl)-N-(4-methyl isophthalic acid; 2,3-thiadiazoles-5-formyl hydrazine)] derivative VI, measure fusing point and
1H NMR determines chemical structure, and the amount of compound VI preparation enlarges by corresponding proportion or dwindles.
3. insecticide, it is characterized in that: claim 1 is described to contain 1,2, and the bishydrazide derivative of 3-thiadiazoles group is gone up the purposes of acceptable assistant in the preparation sterilant with agricultural.
4. sterilant, it is characterized in that: claim 1 is described to contain 1,2, and the bishydrazide derivative of 3-thiadiazoles group is gone up the purposes of acceptable assistant in the preparation sterilant with agricultural.
5. Antiphytoviral medicament, it is characterized in that: claim 1 is described to contain 1,2, and the bishydrazide derivative of 3-thiadiazoles group is gone up the purposes of acceptable assistant in preparation Antiphytoviral medicament with agricultural.
6. a kind of plant activator, it is characterized in that: claim 1 is described to contain 1,2, and the bishydrazide derivative of 3-thiadiazoles group is gone up acceptable assistant is used for Plant diseases and virus disease at preparation plant activator purposes with agricultural.
7. parasiticidal composition, it is characterized in that: claim 1 is described to contain 1,2, the bishydrazide derivative of 3-thiadiazoles group and agricultural go up acceptable assistant and be selected from Chlorpyrifos 94, the inferior Nong in ground, acetamiprid, Affirm (Merck Co.), more visit rhzomorph, Avrmectin, pleocidin, fenvalerate, efficient fenvalerate, Cypermethrin, effective cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, the Beta-cyfloxylate, cyfloxylate, the Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, cyhalothrin, bifenthrin, permethrin, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, acetamiprid, Ti304, imidaclothiz, thiophene worm quinoline, thiophene worm piperazine, thiophene worm amine, MTI-446, clothianadin, Da Tenan, diflubenzuron, young urea goes out, Teflubenzuron, deinsectization is grand, fluorine bell urea, flufenoxuron, the pyridine worm is grand, the Acarus tritici urea, the poisonous insect urea, penfluron, Noviflumuron, flucycloxuron, Novaluron, fluorine pyridine urea, Bay sir6874, piperazine worm urea, Bistrifluron, furans worm hydrazides, the worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides, Rogor, omethoate, SD-1750, acephate, triazophos, Resitox, pyridaphenthione, isazofos, Ro 7-5050, SevinCarbaryl, Aphox, meta-tolyl-N-methylcarbamate (MTMC), isoprocarb, cartap, fenobucarb, leaf disperses, carbaryl, benfuracarb, carbosulfan, cartap, bromopropylate, hexythiazox, azoles mite ester, pyridaben, four mite piperazines, alkynes mite spy, the butyl ether urea, benfuracarb, pyrrole aphid ketone, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, Buprofezin, ethoprophos, fluorine worm nitrile, the desinsection list, disosultap, Flubendiamide, chlorine insect amide or tebufenpyrad, bromothalonil, pyrazine ketone, second mite azoles, tebufenpyrad, the young ketone of rattling away, the pyrrole propyl ether, in the emaricin one or more mix the purposes of using in the preparation sterilant; Claim 1 is described to contain 1,2, the ratio of bishydrazide derivative in composition of 3-thiadiazoles group is 1%-90%, the processing formulation be selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, can disperse dense dose, seed treatment emulsion, aqueous emulsion, in the big granula, granule, microemulsion, oil-suspending agent, finish, seed, suspended emulsion agent, water-soluble granule, soluble thick agent, water-dispersible granules any one with coated pesticidal; Wherein said plant be selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, genseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, melon, really, tea, wild vegetable, bamboo shoots, hops, pepper.
8. desinsection, the composition of antiviral agent, it is characterized in that: claim 1 is described to contain 1,2, the bishydrazide derivative of 3-thiadiazoles group and agricultural go up acceptable assistant and be selected from diazosulfide, tiadinil, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formiate, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, the DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, the first thiophene lures amine or Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, in the allyl isothiazole any one or two kinds of combined preparation become anti-plant virus agent and the purposes in the control viral diseases of plants thereof; Claim 1 is described to contain 1,2, the ratio of bishydrazide derivative in composition of 3-thiadiazoles group is 1%-90%, the processing formulation be selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, can disperse dense dose, seed treatment emulsion, aqueous emulsion, in the big granula, granule, microemulsion, oil-suspending agent, finish, seed, suspended emulsion agent, water-soluble granule, soluble thick agent, water-dispersible granules any one with coated pesticidal; Wherein said plant be selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, genseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, melon, really, tea, wild vegetable, bamboo shoots, hops, pepper.
9. desinsection; The composition of sterilization; It is characterized in that: claimed in claim 1ly contain 1; 2; The bishydrazide derivative of 3-thiadiazoles group and the upper acceptable auxiliary agent of agricultural and be selected from diazosulfide; Tiadinil; Tisocromide; The first thiophene lures amine; The 4-methyl isophthalic acid; 2; 3-thiadiazoles-5-formic acid; The 4-methyl isophthalic acid; 2; 3-thiadiazoles-5-sodium formate; The 4-methyl isophthalic acid; 2,3-thiadiazoles-5-Ethyl formate; The DL-beta-aminobutyric acid; Virazole; Antofine; Ningnanmycin; Tisocromide; The first thiophene lures amine or salicylic acid; Frost urea cyanogen; Thiram; Ziram; Mancozeb; Aliette; Thiophanate-methyl; Bravo; The enemy can be loose; Procymidone; Fenpropidin; Thiophanate methyl; Thiophanate; Metalaxyl-M; Salicylic acid; Flumorph; Dimethomorph; Efficient metalaxyl; Efficient M 9834; Two chlorine zarilamids; Flusulfamide; The first flusulfamide; Thiophene fluorine bacterium amine; Flutolanil; Tecloftalam; Ring propionyl bacterium amine; Cyflufenamid; Fenhexamid; Zarilamid; Silthiopham; Furametpyr; The pyrrole metsulfovax; Mandipropamid; Zoxamide; Fenfuram; Carboxin; Chlozolinate; Iprodione; Fluoxastrobin; Dimoxystrobin; Fluoxastrobin; Kresoxim-methyl; SSF 126; Orysastrobin; ZEN 90160; Pyraclostrobin; Oxime bacterium ester; Enestroburin; Alkene oxime amine; Oxygen ring azoles; Bromuconazole; Cyproconazole; Difenoconazole; Alkene azoles alcohol; Efficient alkene azoles alcohol; Epoxiconazole; RH-7592; Fluquinconazole; Flusilazole; Flutriafol; Own azoles alcohol; Glyoxalin; Plant the bacterium azoles; Metconazole; Nitrile bacterium azoles; Penconazole; Propiconazole; Prothioconazoles; Simeconazoles; Tebuconazole; Tetraconazole; Triadimenol; Triticonazole; Bitertanol; Probenazole; Furidazol; Imazalil; Efficient imazalil; Prochloraz; Fluorine bacterium azoles; Cyazofamid; Fenamidone; The Evil imidazoles; Pefurazoate; Famoxadone; SYP-Z048; Hymexazo; The spirit of Evil frost; Guardian; Grandox fumigant; Octhilinone; Benthiozole; Dodemorph; Butadiene morpholine; Tridemorph; Fenpiclonil; Fludioxonil; Fluazinam; Pyrifenox; Ring pyridine bacterium amine; Boscalid; Fluopicolide; Pyridine bacterium amine; Cyprodinil; The fluorine mepanipyrim; Ferimzone; Mepanipyrim; Phonetic mould amine; Fenarimol; Nuarimol; Chinomethionat; Dithianon; Ethoxyquin; Oxyquinoline; The third oxygen quinoline; Benzene oxygen quinoline; The mould prestige of second; Iprovalicarb; The benzene metsulfovax; Propamocarb; Methasulfocarb; Edifenphos; IBP; Pyrazophos; Tolelofos-methyl; Blasticidin-S; Kasugarnycin; Polyoxin; Polyoxin; Valida; Jinggangmeisu; Streptomysin; Metalaxyl; Furalaxyl; M 9834; Ofurace; Mebenil; Carbendazim; Benomyl; Thiophanate-methyl; Triazolone; Bupirimate; Dimethirimol; The phonetic phenol of second; Difoltan; Captan; Folpet; Vinclozolin; Fluoromide; Dimethachlon; Bravo; Isoprothiolane; Kitazine; Yekuzuo; Pentachloronitrobenzene; Mancozeb; Propineb; Phosethyl-Al; Sulphur; Bordeaux mixture; Copper sulphate; Copper oxychloride; Cuprous oxide; Kocide SD; Metrafenone; Pencycuron; Diclomezin; Rabcide; Pyroquilon; Volution bacterium amine; Tricyclazole; Triforine; The pyridine of many fruits; The hot salt of biguanides; Iminoctadine; Botran; The benzene flusulfamide; The toluene flusulfamide; K-281; Fenaminosulf; Oxolinic acide; Probenazole; Bronopol; Iodomethane; Metham-sodium; Enemy's line ester; Dazomet; Nemamort; Lythidathion; Cadusafos; Fensulfothion; Thionazin; Fenamiphos; Phonamiphos; Dichlofenthion; Isazofos; Fosthietan; Oxamyl; Aldicarb; Carbofuran; Vikane; Dichloropropylene; Dichloro-isonicotinic acid; In the allyl isothiazole any one or two kinds of bactericide combinations are for the preparation of bactericide and their purposes in controlling plant diseases; Claim 1 is described to contain 1,2, the ratio of bishydrazide derivative in composition of 3-thiadiazoles group is 1%-90%, and the formulation of wherein said sterilant is selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, can disperse in dense dose, seed treatment emulsion, aqueous emulsion, big granula, granule, microemulsion, oil-suspending agent, finish, the seed with coated pesticidal, suspended emulsion agent, water-soluble granule, soluble thick agent, water-dispersible granules any one; Wherein said plant be selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, genseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, melon, really, tea, wild vegetable, bamboo shoots, hops, pepper.
10. claim 1 is described contains 1,2, the complete processing that the bishydrazide derivative of 3-thiadiazoles group and commercially available agricultural chemical are combined to form pesticide preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010187048XA CN101891708B (en) | 2009-06-26 | 2010-05-31 | Diacylhydrazine compounds containing 4-methyl-1,2,3-thiadiazole groups, preparation method and application thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910069470.2 | 2009-06-26 | ||
| CNA2009100694702A CN101591308A (en) | 2009-06-26 | 2009-06-26 | A kind ofly contain 1,2, bishydrazide derivative of 3-thiadiazoles active group and its production and use |
| CN201010187048XA CN101891708B (en) | 2009-06-26 | 2010-05-31 | Diacylhydrazine compounds containing 4-methyl-1,2,3-thiadiazole groups, preparation method and application thereof |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103438141A Division CN102432563B (en) | 2009-06-26 | 2010-05-31 | Dihydrazide compounds containing 4-methyl-1,2,3-thiadiazole group, and preparation method and application of dihydrazide compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101891708A true CN101891708A (en) | 2010-11-24 |
| CN101891708B CN101891708B (en) | 2012-02-08 |
Family
ID=41406208
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100694702A Pending CN101591308A (en) | 2009-06-26 | 2009-06-26 | A kind ofly contain 1,2, bishydrazide derivative of 3-thiadiazoles active group and its production and use |
| CN2011103438141A Expired - Fee Related CN102432563B (en) | 2009-06-26 | 2010-05-31 | Dihydrazide compounds containing 4-methyl-1,2,3-thiadiazole group, and preparation method and application of dihydrazide compounds |
| CN201010187048XA Expired - Fee Related CN101891708B (en) | 2009-06-26 | 2010-05-31 | Diacylhydrazine compounds containing 4-methyl-1,2,3-thiadiazole groups, preparation method and application thereof |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100694702A Pending CN101591308A (en) | 2009-06-26 | 2009-06-26 | A kind ofly contain 1,2, bishydrazide derivative of 3-thiadiazoles active group and its production and use |
| CN2011103438141A Expired - Fee Related CN102432563B (en) | 2009-06-26 | 2010-05-31 | Dihydrazide compounds containing 4-methyl-1,2,3-thiadiazole group, and preparation method and application of dihydrazide compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN101591308A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102007927A (en) * | 2010-12-07 | 2011-04-13 | 陕西韦尔奇作物保护有限公司 | Sterilization composition containing triflumizole |
| CN102633747A (en) * | 2012-04-05 | 2012-08-15 | 南开大学 | 5-methyl-1, 2, 3-thiadiazole bishydrazide derivatives as well as preparation method and application thereof |
| CN103483288A (en) * | 2013-10-12 | 2014-01-01 | 南开大学 | 3,4-dichloroisothiazole containing bishydrazide compounds as well as preparation method and application thereof |
| CN105165893A (en) * | 2015-10-27 | 2015-12-23 | 宁波三江益农作物保护有限公司 | Plant sterilization composite |
| CN111548320A (en) * | 2019-10-09 | 2020-08-18 | 贵州大学 | 1, 3, 4-oxadiazole hydrazide compounds and preparation method and application thereof |
| CN114835696A (en) * | 2022-05-24 | 2022-08-02 | 贵州医科大学 | Phthalide hydrazide compound, preparation method and application thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857580B (en) * | 2010-04-27 | 2011-11-30 | 华东交通大学 | Thiadiazole derivative containing hydroxy and xanthic acid and preparation method and application thereof |
| CN102633746A (en) * | 2012-04-05 | 2012-08-15 | 南开大学 | Di-hydrazide derivatives containing 5-methyl-1, 2, 3-thiadizole and preparation method and application of di-hydrazide derivatives containing 5-methyl-1, 2, 3-thiadizole |
| CN103163246B (en) * | 2013-03-18 | 2014-07-23 | 中国农业科学院烟草研究所 | Method for detecting residual quantity of methyl thiadiazole induced amine in tobacco and fruits and vegetables by SPE-HPLC/UV (Solid Phase Extraction-High Performance Liquid Chromatography/ultraviolet) |
| CN103483313A (en) * | 2013-09-03 | 2014-01-01 | 南开大学 | Novel hydrazide derivatives as well as preparation method and application thereof |
| CN108947866A (en) * | 2018-08-11 | 2018-12-07 | 安康学院 | N-(2- methyl -3- Phenylbenzoyl)-N '-tertiary butyl hydrazine and its synthetic method |
| CN113121426B (en) * | 2021-03-12 | 2023-01-06 | 广西大学 | Synthesis method of myrtenal aldehyde group dihydrazide compounds with fungal inhibition activity |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5482962A (en) * | 1994-07-22 | 1996-01-09 | Rohm And Haas Company | Insecticidal N,N'-disubstituted-N-N'-diacylhydrazines |
| CN1180297A (en) * | 1995-03-31 | 1998-04-29 | 日本农药株式会社 | Agricultural and horticultural disease controller and method for controlling diseases |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008127334A (en) * | 2006-11-21 | 2008-06-05 | Mitsui Chemicals Inc | Method for preventing disease and insect damage of plant |
| CN101343269B (en) * | 2008-08-28 | 2010-10-13 | 南开大学 | 1,2,3-thiadiazoles derivants, synthesis and use thereof |
-
2009
- 2009-06-26 CN CNA2009100694702A patent/CN101591308A/en active Pending
-
2010
- 2010-05-31 CN CN2011103438141A patent/CN102432563B/en not_active Expired - Fee Related
- 2010-05-31 CN CN201010187048XA patent/CN101891708B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5482962A (en) * | 1994-07-22 | 1996-01-09 | Rohm And Haas Company | Insecticidal N,N'-disubstituted-N-N'-diacylhydrazines |
| CN1180297A (en) * | 1995-03-31 | 1998-04-29 | 日本农药株式会社 | Agricultural and horticultural disease controller and method for controlling diseases |
Non-Patent Citations (1)
| Title |
|---|
| 《现代农药》 20040430 冯坚 双酰肼类昆虫生长调节剂研究开发进展 4-8 第3卷, 第2期 2 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102007927A (en) * | 2010-12-07 | 2011-04-13 | 陕西韦尔奇作物保护有限公司 | Sterilization composition containing triflumizole |
| CN102007927B (en) * | 2010-12-07 | 2013-08-14 | 陕西韦尔奇作物保护有限公司 | Sterilization composition containing triflumizole |
| CN102633747A (en) * | 2012-04-05 | 2012-08-15 | 南开大学 | 5-methyl-1, 2, 3-thiadiazole bishydrazide derivatives as well as preparation method and application thereof |
| CN103483288A (en) * | 2013-10-12 | 2014-01-01 | 南开大学 | 3,4-dichloroisothiazole containing bishydrazide compounds as well as preparation method and application thereof |
| CN103483288B (en) * | 2013-10-12 | 2016-03-30 | 南开大学 | One class 3,4-bis-chloroisothiazole bishydrazide compounds and its production and use |
| CN105165893A (en) * | 2015-10-27 | 2015-12-23 | 宁波三江益农作物保护有限公司 | Plant sterilization composite |
| CN111548320A (en) * | 2019-10-09 | 2020-08-18 | 贵州大学 | 1, 3, 4-oxadiazole hydrazide compounds and preparation method and application thereof |
| CN114835696A (en) * | 2022-05-24 | 2022-08-02 | 贵州医科大学 | Phthalide hydrazide compound, preparation method and application thereof |
| CN114835696B (en) * | 2022-05-24 | 2024-03-05 | 贵州医科大学 | Phthalide hydrazide compound and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102432563A (en) | 2012-05-02 |
| CN101891708B (en) | 2012-02-08 |
| CN101591308A (en) | 2009-12-02 |
| CN102432563B (en) | 2013-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102432563B (en) | Dihydrazide compounds containing 4-methyl-1,2,3-thiadiazole group, and preparation method and application of dihydrazide compounds | |
| CN102225918B (en) | One class 1,2,3-thiadiazole formoxyl ureide compound and its production and use | |
| CN102174030B (en) | 5-methyl-1,2,3-thiadiazole-4-formoxyl urea compounds, and preparation method and application thereof | |
| CN101973959A (en) | 4-methyl-1,2,3-thiadiazole-5-formyl urea compounds and preparation method and application thereof | |
| CN105622422A (en) | Bromohexahydro indanone compound and preparation method and application thereof | |
| CN103497182A (en) | 3,4-dichloro isothiazole derivative containing 4,5-dihydro thiazole alkyd resin and preparation method and application thereof | |
| CN103483287B (en) | 3,4-dichloroisothiazole containing bisamide compounds as well as preparation method and application thereof | |
| CN102603669B (en) | Derivatives of alpha-methoxyl imino-5-methyl-1,2,3-thiadiazole-4- carboxylic acid methyl ester and preparation methods and uses thereof | |
| CN104650061A (en) | Thiazole oxime ether compounds as well as preparation method and use thereof | |
| CN101891710B (en) | 4-halogenated methyl-1,2,3-thiadiazole compounds and preparation method and application thereof | |
| CN102382108B (en) | Tetrazole compounds containing 1,2,3-bismuththiol methylene, preparation methods for same and application thereof | |
| CN101899042A (en) | 4-substituted-1,2,3-thiadiazole formoxyl ureide compound, preparation method and application thereof | |
| CN101891709B (en) | 5-halogenated methyl-1,2,3-thiadiazole compound and preparation method and use thereof | |
| CN102633747A (en) | 5-methyl-1, 2, 3-thiadiazole bishydrazide derivatives as well as preparation method and application thereof | |
| CN102816158B (en) | 5-methyl-1,2,3-thiadiazole-1,3,4-oxadiazole derivatives, and preparation method and application thereof | |
| CN102816135B (en) | 5-methyl-1,2,3-thiadiazole-containing 1,3,4-thiadiazole derivatives and their preparation method and use | |
| CN101921244B (en) | Derivative of 4-methyl-1,2,3-thiadiazole containing 4-(1,1,2,2-tetrafluoroethoxy)-3,5-dichlorobenzene amino and synthesis method and application thereof | |
| CN103641795B (en) | One class contains acetophenone derivs of 1,2,3-thiadiazoles and its production and use | |
| CN103193769A (en) | 4-methyl-1,2,3-thiadiazole-5-triazole compound as well as preparation method and use thereof | |
| CN103483288B (en) | One class 3,4-bis-chloroisothiazole bishydrazide compounds and its production and use | |
| CN102633745B (en) | Alpha-methoxy imino group-4-methyl-1, 2, 3-thiadiazole-5-methyl carboxylic ester derivatives and preparation method and application thereof | |
| CN104496980A (en) | Novel thiazole heterocyclic compound as well as preparation method and application thereof | |
| CN107602547A (en) | Heterocycle triazole derivative and its production and use | |
| CN103012392A (en) | Pyridine derivatives containing 1.2,3-thiadiazole, and preparation method and application thereof | |
| CN102633746A (en) | Di-hydrazide derivatives containing 5-methyl-1, 2, 3-thiadizole and preparation method and application of di-hydrazide derivatives containing 5-methyl-1, 2, 3-thiadizole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120208 Termination date: 20120531 |