CN102225918A - 1,2,3-thiadiazole formyl urea compounds as well as preparation method and application thereof - Google Patents
1,2,3-thiadiazole formyl urea compounds as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides 1,2,3-thiadiazole formyl urea compounds as well as a preparation method and application thereof, relating to heterocyclic compounds containing 1,2,3-thiadiazole. The 1,2,3-thiadiazole formyl urea compounds have chemical general formulae as shown in V and VII. The invention discloses the chemical general formulae and a synthesis method of the compounds, application of the compounds as insecticides, disinfectants, plant virus resisting agents and plant activating agents and a process in which the compounds are mixed with agriculturally acceptable auxiliaries or synergists for preparation of insecticides, disinfectants, plant virus resisting agents and plant activating agents. The invention also discloses application that the compounds are combined with commercial insecticides, disinfectants, plant virus resisting agents and plant activating agents to be used in prevention and treatment of diseases, insect pests and virus diseases in the fields of agriculture, forestry and health and a preparation method of the compositions.
Description
Technical field
Technical scheme of the present invention relates to and contains the 1,2-diazole compound, is specifically related to high reactivity 4-and replaces-1,2,3-thiadiazole formoxyl ureide compound and two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds.
Background technology
Benzoyl urea insect growth regulator(IGR) (being called for short BPUs class insect growth regulator(IGR)) is eco-friendly green pesticide; biological activity with moulting hormone antagonist; can increase the catalytic activity of chitinase; quicken chitinous enzymolysis process, also can suppress the activity of chitin synthetase (CS).For larva; if CS activity inhibited; not only suppressed the prolongation of chitin chain; also weakened provide protection to the O-glycosides key; interferencing protein and chitinous combination; the havoc insect molting; stop peritrophic formation; influence normal development; the result makes the soft shortage hardness of epidermis, and finally causing insect dehydration death or becoming lopsided pupa death, the epidermis of insect is its " bone "; also be the vital tissue of insect gaseous interchange, do not have the not normal insect of " bone " and gaseous interchange function just with the patient who suffers from richets and dyspnoea.For ovum, if the CS activity is suppressed, then influence DNA and protein metabolism in the respiratory metabolism of ovum and the fetal development, make larva shortage chitin in the ovum and death immediately after can not hatching or hatch, so it also is a kind of apholate (Cohen, et al.Annu Rev Entomo, 1987,2 (3): 71-93; Merzendorfer.Comp.Physiol.B.2006.176:1-15; Liang Ying, etc. agricultural chemicals, 2009,48 (9): 625-632; Matsumura et al.Pestic.Biochem.Physiol., doi:10.1016/j.pestbp.2009.101); Because its unique mechanism of action is drawn the main limitation of this class medicament and is: its insecticidal spectrum is narrow, can not doublely simultaneously control with the various pests on a kind of crop; Desinsection speed is Pest Control rapidly slowly, still can get food after insect poisons and peel up to next time, and the lethal time of lepidopterous insects is needed 2-7d, and quick-acting is poor; Growth to aquatic crustaceans biology is unfavorable.There is more than 10 commercialization kind to appear on the market at present.But because it is water-soluble extremely low, the lasting period long and be subjected to the peasant welcome (Mi Na, etc. world's agricultural chemicals, 2009,31 (supplementary issue II): 24-26).Guide's general structure of BPUs insecticides is seen formula 1:
The general structure of formula 1BPUs insecticides
In commercial kind, the introducing halogen obtains the good commercialization kind of insecticidal activity diflubenzuron on benzoyl, young urea etc. goes out; On the arylamine ring, introduce CF
3, OCF
3, OCF
2CF
2Deng obtain that the deinsectization of commercialization kind is grand, fluorine bell urea etc.; On the arylamine ring, introduce a plurality of halogen atoms and develop commercialization kind Teflubenzuron; Introduce to replace in the contraposition of arylamine ring that virtue (mix) oxygen base develops that commercialization kind pyridine worm is swelled, flufenoxuron etc.The benzoyl urea compound of halogen after especially the F atom is introduced demonstrates good biological activity (Zhang Jian, et al.J.Agric.Food Chem., 2009,58 (5): 2736-2740) to lepidopterous cotton-plant pest-insects and vegetables pest.Therefore, the main direction of BPUs class chitin synthesis inhibitor initiative is to introduce halogen to improve the contact toxicity of BPUs class chitin synthesis inhibitor; Introduce strong polar group with inhale in improving or in ooze insecticidal activity.
The structure of BPUs class chitin synthesis inhibitor system is derived and is mainly carried out on two aromatic nucleus and urea bridge.The research of aromatic ring is mainly concentrated on the heterocycle of phenyl ring and other replacements, but relevant 1,2, bibliographical information is not seen in the introducing of 3-thiadiazoles ring.And 1,2, the 3-thiadiazoles derivative has wide biological activity (Bakulev, et al.Newyork:John Wiley﹠amp; Sons, Inc, 2004), cotton defoliant---disleave spirit (N-phenyl-N-1,2,3-thiadiazoles-5-urea that agriculture field is used, TDZ), plant activator---Acibenzolar (phendioxin, 2,3-thiadiazoles-7-thiocarboxylic acid methyl esters, BTH), rice field sterilant---tiadinil (3 '-chloro-4,4 '-dimethyl-1,2,3-thiadiazoles-5-formylaniline, TDL) all be 1,2, the derivative of 3-thiadiazoles.Consider that halogen is bioactive important activity group, in molecule, introduce halogen atom and become novel pesticide molecular designing synthetic main approaches and means, in commercial halo pesticide species, majority comprises the Cl atom, but the introducing of Br and I also can be played unexpected effect, just comprise the I atom in the Ryanicide acceptor inhibitor Flubendiamide molecule of for example succeeding in developing recently, and the introducing of F atom often also can improve the biological activity of molecule, and the sterilant flumorph replaces back initiative invention with the Cl atom in the dimethomorph molecule with the F atom.
Therefore, in order to seek 1 of high biological activity more, 2,3-thiadiazole new compound, the principle that the present invention utilizes pesticide molecule design with an aromatic ring of benzoyl urea with 1,2, the 3-thiadiazoles replaces, and introduces halogen atom simultaneously in molecule, and design has been synthesized a class high reactivity 4-and replaced-1,2,3-thiadiazole formoxyl ureide compound and two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds, carried out the bioactive screening and the evaluation of system simultaneously, provide candidate compound in the hope of initiative research for novel pesticide.
Summary of the invention
Technical problem to be solved by this invention is: provide new high reactivity 4-to replace-1,2,3-thiadiazole formoxyl ureide compound and two (4-replacement-1,2,3-thiadiazoles-5-formyl urea) synthetic method of compounds, provide this compounds to suppress the biological activity and the measuring method thereof of agricultural and gardening and forestry plant pathogen, the middle application of these compounds in agriculture field and gardening field and field of forestry is provided simultaneously.
The present invention solves this technical problem the technical scheme that is adopted: the high reactivity 4-with agriculture field, gardening field, field of forestry insecticidal activity, fungicidal activity, anti-phytoviral activity, inducing plant generation anti-disease activity, insect growth regulator activity replaces-1,2, the chemical structure of general formula of 3-thiadiazole formoxyl ureide compound is seen formula V:
Wherein, R
1For being selected from following substituting group: H, CH
3, CF
3, Ph, CHF
2, CH
2X, described X are halogen atom F, Cl, Br, I, cyclopropyl, substituted-phenyl, substituted heterocycle aryl; R
2, R
3, R
4, R
5For being selected from following substituting group: H, F, Cl, Br, I, CF
3, CCl
3, OCF
3, allyl group, propargyl, aldehyde radical, hydroxyl, amido, itrile group, ester group, carboxyl, C1-C12 cycloalkyl, cycloalkenyl group, cycloalkynyl radical, various straight or branched that 1 to 10 halogen atom replaces or cyclic alkyl, thiazolinyl, alkynyl, Ph, the CHF of containing of straight or branched alkyl, thiazolinyl, alkynyl, C3-C12
2, CH
2X or-OR
6Group, described X is the group of halogen atom F, Cl, Br, I, cyclopropyl, substituted-phenyl, described R
6Be the cycloalkyl of the straight or branched that is selected from C1-C12 or cyclic alkyl, thiazolinyl, alkynyl, C3-C12, cycloalkenyl group, cycloalkynyl radical, various straight or branched that 1 to 10 halogen atom replaces or cyclic alkyl, thiazolinyl, the alkynyl of containing; Alkyl wherein, thiazolinyl, alkynyl are selected from the direct-connected or side chain of C1-C12 or cyclic alkyl, thiazolinyl, alkynyl, these alkyl, thiazolinyl, alkynyl contain 1 to 10 halogen atom, various substituted aryl or the heterocyclic aryl that contains 1 to 10 halogen atoms, halogen atom wherein is meant F, Cl, Br, I atom, can directly link with aromatic ring, also can directly be connected with alkyl, thiazolinyl, the alkynyl on the aromatic ring, described alkyl, thiazolinyl, alkynyl are selected from the direct-connected or side chain of C1-C12 or cyclic alkane, thiazolinyl, alkynyl; Described aryl is meant the phenyl of various replacements or pyridyl, thiazolyl, thiadiazolyl group, pyrimidyl, thienyl, triazolyl, tetrazole base, pyrryl, furyl, pyrazinyl, thiazinyl, the triazinyl of various replacements; R
2, R
3, R
4, R
5The phenyl that replaces also is selected from substituted benzene benzothiazolyl, substituted anthraquinone base, substituted naphthyl.
High reactivity 4-of the present invention replaces-1,2, and the synthetic method of 3-thiadiazole formoxyl ureide compound V is as follows:
Wherein, R
1Be selected from following substituting group: H, CH
3, CF
3, Ph, CHF
2, CH
2X, described X are halogen atom F, Cl, Br, I, cyclopropyl, substituted-phenyl, substituted heterocycle aryl; R
2, R
3, R
4, R
5Be selected from following substituting group: H, F, Cl, Br, I, CF
3, CCl
3, OCF
3, allyl group, propargyl, aldehyde radical, hydroxyl, amido, itrile group, ester group, carboxyl, C1-C12 cycloalkyl, cycloalkenyl group, cycloalkynyl radical, various straight or branched that 1 to 10 halogen atom replaces or cyclic alkyl, thiazolinyl, alkynyl, Ph, the CHF of containing of straight or branched alkyl, thiazolinyl, alkynyl, C3-C12
2, CH
2X or-OR
6Group, described X is the group of halogen atom F, Cl, Br, I, cyclopropyl, substituted-phenyl, described R
6Be the cycloalkyl of the straight or branched that is selected from C1-C12 or cyclic alkyl, thiazolinyl, alkynyl, C3-C12, cycloalkenyl group, cycloalkynyl radical, various straight or branched that 1 to 10 halogen atom replaces or cyclic alkyl, thiazolinyl, the alkynyl of containing; Alkyl wherein, thiazolinyl, alkynyl are selected from the direct-connected or side chain of C1-C12 or cyclic alkyl, thiazolinyl, alkynyl, these alkyl, thiazolinyl, alkynyl contain 1 to 10 halogen atom, various substituted aryl or the heterocyclic aryl that contains 1 to 10 halogen atoms, halogen atom wherein is meant F, Cl, Br, I atom, can directly link with aromatic ring, also can directly be connected with alkyl, thiazolinyl, the alkynyl on the aromatic ring, described alkyl, thiazolinyl, alkynyl are selected from the direct-connected or side chain of C1-C12 or cyclic alkane, thiazolinyl, alkynyl; Described aryl is meant the phenyl of various replacements or pyridyl, thiazolyl, thiadiazolyl group, pyrimidyl, thienyl, triazolyl, tetrazole base, pyrryl, furyl, pyrazinyl, thiazinyl, the triazinyl of various replacements; R
2, R
3, R
4, R
5The phenyl that replaces also is selected from substituted benzene benzothiazolyl, substituted anthraquinone base, substituted naphthyl.
High reactivity 4-with agricultural, gardening and forestry fungicidal activity replaces-1,2, and two in the 3-thiadiazole formoxyl ureide compound (4-replaces-1,2,3-thiadiazoles-5-formyl urea) chemical structure of general formula of compounds is seen formula VII:
Wherein, wherein, R
1For being selected from following substituting group: H, CH
3, CF
3, Ph, CHF
2, CH
2X, described X are halogen atom F, Cl, Br, I, cyclopropyl, substituted-phenyl, substituted heterocycle aryl; Q is for being selected from benzene-1,2-two bases, benzene-1,3-two bases, benzene-1,4-two bases, pyridine-2,6-two bases, 2-oil of mirbane-1,4-two bases, naphthalene-1,8-two bases, 2-cyano group vinyl cyanide-1,1-two bases, 4-methylbenzene-1,2-two bases, 4-phenyl-1,3,5-triazine-2,6-two bases, hexamethylene-1,2-two bases, 4-oil of mirbane-1,2-two bases, 4-methylbenzene-1,3-two bases, dicyclohexyl methylene radical-4,4 '-two bases, anthraquinone-1,4-two bases, 4,4-dimethyl cyclohexane-1-base-3-methylene radical-, pyridine-2,3-two bases, pyridine-2,4-two bases, pyridine-2,5-two bases, pyridine-2,6-two bases, pyridine-3,4-two bases, pyridine-3,5-two bases, thiophene-2,3-two bases, thiophene-2,4-two bases, thiophene-2,5-two bases, thiophene-3,4-two bases, furans-2,3-two bases, furans-2,4-two bases, furans-2,5-two bases, furans-3,4-two bases, 3,4-diaminostilbene, 2, the 5-oxadiazole, 2,3-diamino-5,6-dicyano pyrazine, 2, the group of aromatic diamines such as 3-diamino-5-bromo-pyrazine or heteroaromatic diamines.
Two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) of the present invention synthetic method of compounds VII is as follows:
Wherein, wherein, R
1For being selected from following substituting group: H, CH
3, CF
3, Ph, CHF
2, CH
2X, described X are halogen atom F, Cl, Br, I, cyclopropyl, substituted-phenyl, substituted heterocycle aryl; Q is for being selected from benzene-1,2-two bases, benzene-1,3-two bases, benzene-1,4-two bases, pyridine-2,6-two bases, 2-oil of mirbane-1,4-two bases, naphthalene-1,8-two bases, 2-cyano group vinyl cyanide-1,1-two bases, 4-methylbenzene-1,2-two bases, 4-phenyl-1,3,5-triazine-2,6-two bases, hexamethylene-1,2-two bases, 4-oil of mirbane-1,2-two bases, 4-methylbenzene-1,3-two bases, dicyclohexyl methylene radical-4,4 '-two bases, anthraquinone-1,4-two bases, 4,4-dimethyl cyclohexane-1-base-3-methylene radical-, pyridine-2,3-two bases, pyridine-2,4-two bases, pyridine-2,5-two bases, pyridine-2,6-two bases, pyridine-3,4-two bases, pyridine-3,5-two bases, thiophene-2,3-two bases, thiophene-2,4-two bases, thiophene-2,5-two bases, thiophene-3,4-two bases, furans-2,3-two bases, furans-2,4-two bases, furans-2,5-two bases, furans-3,4-two bases, 3,4-diaminostilbene, 2, the 5-oxadiazole, 2,3-diamino-5,6-dicyano pyrazine, 2, the group of aromatic diamines such as 3-diamino-5-bromo-pyrazine or heteroaromatic diamines.
Specifically be divided into following steps:
A. intermediate 4-replaces-1,2, the preparation of 3-thiadiazole formoxyl chlorine I:
Intermediate 4-replaces-1,2,3-thiadiazole formoxyl chlorine I prepares as follows: 0.067 mole intermediate 4-is replaced-1,2,3-thiadiazoles 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, yield 85% under 2000Pa, intermediate 4-replaces-1,2, the sealing of 3-thiadiazole formoxyl chlorine is kept in the moisture eliminator standby, and intermediate 4-replaces-1,2, the amount of 3-thiadiazole formoxyl chlorine I preparation enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles.
B. intermediate 4-replaces-1,2, the preparation of 3-thiobizole formanide II:
In 500 milliliters two-mouth bottle, the ammoniacal liquor that adds 30 milliliter 25%, 5 milliliters triethylamine, 50 milliliters tetrahydrofuran (THF), the intermediate 4-replacement-1,2 that the Dropwise 5 gram dilute through 10 milliliters of tetrahydrofuran (THF)s under the cooling of ice bath and mechanical stirring, 3-thiadiazole formoxyl chlorine I, dropwised in 15 minutes, ice bath continues down to stir 2 hours, at room temperature stirs then 7 hours; After reaction finishes, use the separating funnel separatory, 15 milliliters of tetrahydrofuran (THF) aqueous layer extracted 3 times, merging organic layer, spend the night with anhydrous sodium sulfate drying, suction filtration is removed anhydrous sodium sulphate, and rotary evaporation removes and desolvates, and the adularescent chip solid generates, for intermediate 4-replaces-1,2,3-thiobizole formanide II; The amount of synthetic compound II enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles.
C. intermediate 4-replaces-1,2, the preparation of 3-thiadiazole formoxyl based isocyanate III:
Get 100 milliliters there-necked flask, add 2 gram intermediate 4-and replace-1,2,1 of 3-thiobizole formanide II and 15 milliliters, the 2-ethylene dichloride stirs, acid amides is uniformly dispersed in solvent, drip 4.3 grams through 5 milliliter 1 with dropping funnel under ice bath, the oxalyl chloride that the 2-ethylene dichloride diluted dropwised in 30 minutes, stirred 1 hour under the room temperature then, reheat to 80 degree centigrade backflow 7 hours, reaction solution becomes muddiness from white and changes shallow yellow transparent solution into, and heating back color deepens gradually; After reaction finished, rotary evaporation removed and desolvates to such an extent that intermediate 4-replaces-1,2, and 3-thiadiazole formoxyl based isocyanate III need not be further purified and be directly used in subsequent reactions; The amount of synthetic compound III enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles.
D. high reactivity 4-replaces-1,2, the preparation of 3-thiadiazole formoxyl ureide compound V:
In 100 milliliters of round-bottomed flasks, add aminated compounds IV that 2.7 mmole halogens replace and 20 milliliter 1, the 2-ethylene dichloride, stir and drip 3 mmole intermediate 4-replacement-1 down, 2,3-thiadiazole formoxyl based isocyanate III dropwised in 15 minutes, produced precipitation immediately, at room temperature stirred 8 hours, after reaction finishes, leave standstill suction filtration separate solid and solvent, solid is product V, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; With the pure product calculated yield of gained, measure fusing point and
1The mensuration of H NMR, the amount of synthetic compound V enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles; Compound chemical structure sees Table 1 and table 2.
E. the preparation of high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII:
In 100 milliliters of round-bottomed flasks, add diamine compounds H
2N-Q-NH
2VI, drip 1 again, the 2-ethylene dichloride and be stirred to aminated compounds just fully the dissolving till, under agitation drip 3 mmole 4-methyl isophthalic acids then, 2,3-thiadiazoles-5-formyl radical isocyanic ester III (about 0.5 gram) (diamines: isocyanic ester is 0.45: 1) in molar ratio, dropwised in 20 minutes, reflux is 1 hour then, at room temperature stirs 8 hours afterreactions and finishes, the standing and reacting mixture, suction filtration is collected solid and is crude product VII; Filtrate is put into refrigerator and cooled has solid to separate out after but, and combining solid and washing are dry, and be 1: 3 ethyl acetate with volume ratio: petroleum ether gets the pure product of product; With the pure product calculated yield of gained, measure fusing point and
1The mensuration of HNMR, the amount of synthetic compound VII enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles; Compound chemical structure sees Table 1 and table 2.
F. high reactivity 4-replaces-1,2,3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea)
The mensuration that compounds VII influences the pathogenic fungi growth activity:
High reactivity 4-of the present invention replaces-1,2,3-thiadiazole formoxyl ureide compound V and high reactivity are two, and (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII sterilization or bacteriostatic activity adopt 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 on cultivation in 24 ± 1 degrees centigrade of constant incubators, 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); GZ: fusarium graminearum (Gibberella zeae); PI: phytophthora infestans (Phytophthora infestans (Mont.) de Bary); PP: ring rot of apple bacterium (Physalospora piricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); RC: cereal rhizoctonia (Rhizoctonia cerealis); SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum), these pathogenic fungies can be represented the kind of most of pathogenic bacteria of the actual generation in field in China's agriculture production.
G. high reactivity 4-of the present invention replaces-1,2, and 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII is to the mensuration of small cabbage moth insecticidal activity:
High reactivity 4-of the present invention replaces-1,2, and compounds VII is as follows to the screening method of the insecticidal activity of small cabbage moth for 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea): adopt the blade medicine embrane method; Sample carries out active primary dcreening operation with 200 mg/litre earlier.Former medicine is earlier with the small amount of acetone dissolving, and with 0.5 ‰ Triton-100 dilution, 0.5 ‰ Triton-100 water are contrast then, and each concentration repeats for 4 times, and about 10 of each re-treatments try worm; Get fresh free of contamination cabbage leaves, in the soup of series concentration gradient, soaked 10 seconds, after indoor drying (about 2 hours), put into the culture dish of 9 centimetres of diameters, insert 2 initial stage in age of the small cabbage moth larva of big or small basically identical respectively; Tighten with bungee and to be placed in the small cabbage moth constant temperature insectary check result and calculation correction mortality ratio after 96 hours or 120 hours; Touching polypide with little writing brush or tweezers, can not coordinated movement be dead; With the positive contrast of young urea of going out.
H. high reactivity 4-of the present invention replaces-1,2, and 3-thiadiazole formoxyl ureide compound and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds is to the mensuration of mosquito larvae insecticidal activity:
High reactivity 4-of the present invention replaces-1,2,3-thiadiazole formoxyl ureide compound V and high reactivity are two, and (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII is as follows to the screening method of the insecticidal activity of mosquito larvae: culex pipiens pallens (Culexpipiens pallens), the normal population of indoor feeding; Take by weighing 2.5 milligrams of test compounds in the penicillin medicine bottle, add 10 milliliters of acetone, vibration dissolving sample is mixed with the mother liquor of 250 mcg/ml; Pipette 1 milliliter of mother liquor in 100 ml beakers that fill 39 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, its liquor strength is 5 mcg/ml.It is 25 degrees centigrade of cultivations that the solution of handling well is put into standard treatment chamber maintenance temperature together with the beaker of mosquito larvae, begin check result after 24 hours, add a small amount of mosquito feed and sucking-off tumbler every day, replenish moisture evaporated (5 milliliters/day) in the beaker, all dead or pupate up to mosquito larvae; Most larvas pupated in 8 days; With the aqueous solution that contains 1 milliliter of acetone is blank; With the positive contrast of young urea of going out.
The invention has the beneficial effects as follows: the present invention replaces-1 to high reactivity 4-, 2,3-thiadiazole formoxyl ureide compound V and high reactivity are two, and (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII has carried out the optimization of first guide structure, and the synthetic new compound carried out the screening of bacteriostatic activity and insecticidal activity, this compounds can be used to prevent and treat agriculture field and the Plant diseases in field of forestry and gardening field or the control of insect pest of the plant.
The present invention will more specifically describe high reactivity 4-by specific preparation and biological activity determination embodiment and replace-1,2,3-thiadiazole formoxyl ureide compound V and high reactivity are two, and (4-replaces-1,2,3-thiadiazoles-5-formyl urea) synthetic and biological activity and the application thereof of compounds VII, described embodiment only is used for specific description the present invention and unrestricted the present invention, especially its biological activity only illustrate, and unrestricted this patent, embodiment is as follows:
Embodiment 1
Intermediate 4-replaces-1,2, the preparation of 3-thiobizole formanide II
In 500 milliliters two-mouth bottle, the ammoniacal liquor that adds 30 milliliter 25%, 5 milliliters triethylamine, 50 milliliters tetrahydrofuran (THF), the Dropwise 5 gram replaces-1,2 through the high reactivity 4-that 10 milliliters of tetrahydrofuran (THF)s diluted under ice bath cooling and mechanical stirring, 3-thiadiazole formoxyl chlorine I, dropwised in 15 minutes, ice bath continues down to stir 2 hours, at room temperature stirs then 7 hours.After reaction finishes, use the separating funnel separatory, 15 milliliters of tetrahydrofuran (THF) aqueous layer extracted 3 times, merge organic layer, spend the night with anhydrous sodium sulfate drying, suction filtration rear filtrate rotary evaporation remove desolvate the white plates solid, be intermediate 4-and replace-1,2,3-thiobizole formanide II.
Embodiment 2
Intermediate 4-replaces-1,2, the preparation of 3-thiadiazole formoxyl based isocyanate III
Get 100 milliliters there-necked flask, add 2 gram intermediate 4-and replace-1,2,3-thiobizole formanide II and 15 milliliter 1, the 2-ethylene dichloride stirs, it is uniformly dispersed in solvent, drip 4.3 grams through 5 milliliter 1 under ice bath, the oxalyl chloride that the 2-ethylene dichloride diluted dropwised in 30 minutes, stirred 1 hour under the room temperature then, reheat to 80 degree centigrade backflow 7 hours, reaction solution becomes muddiness from white and changes shallow yellow transparent solution into, and heating back color deepens gradually.After reaction finished, rotary evaporation removed and desolvates to such an extent that intermediate 4-replaces-1,2, and 3-thiadiazole formoxyl based isocyanate III need not be further purified and be directly used in subsequent reactions.
Embodiment 3
Compound GDD-52:N-[3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenyl]-synthesizing of N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea reach the structure evaluation
In 100 milliliters of round-bottomed flasks, add 2.7 mmoles 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) aniline and 20 milliliter 1, the 2-ethylene dichloride stirs and drips 3 mmole 4-methyl isophthalic acids, 2 down, 3-thiadiazoles-5-formyl radical isocyanic ester, dropwised in 15 minutes, and produced precipitation immediately, at room temperature stirred 8 hours, after reaction finishes, leave standstill, suction filtration gets solid product, and the filtrate rotary evaporation removes and desolvates, with volume ratio 1: 3 ethyl acetate: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; White crystal, fusing point: 168-170 degree centigrade, yield 74%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.89 (s, 3H, CH
3), 8.02 (s, 2H, Ar-H), 10.52 (s, 1H, NH), 11.73 (s, 1H, NH).
Embodiment 4
Synthetic and the structure of compound GDD-91F:N-(1,3,4-thiadiazoles-2-yl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 2-amidos-1,3,4-thiadiazoles and 20 milliliter 1, the 2-ethylene dichloride, be stirred to 2-amido-1,3, the 4-thiadiazoles dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 212-214 degree centigrade, yield 85%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.82 (s, 3H, CH
3), 9.23 (s, 1H, Ar-H), 11.72 (s, 1H, NH), 11.83 (s, 1H, NH).
Embodiment 5
Synthetic and the structure of compound GDD-92:N-(phenyl aldehyde-4-yl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 4-amido phenyl aldehydes and 20 milliliter 1, the 2-ethylene dichloride, being stirred to 4-amido phenyl aldehyde dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: greater than 240 degrees centigrade, yield 95%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.83 (s, 3H, CH
3), 7.80 (d, 2H, J=8.4Hz, Ar-H), 7.92 (d, 2H, J=8.8Hz, Ar-H), 9.92 (s, 1H, CHO), 10.57 (s, 1H, NH), 11.58 (s, 1H, NH).
Embodiment 6
Synthetic and the structure of compound GDD-93:N-(2-hydroxy phenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 2-amino-phenols and 20 milliliter 1, the 2-ethylene dichloride, being stirred to the 2-amino-phenol dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 186-188 degree centigrade, yield 93%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.88 (s, 3H, CH
3), 6.99-6.83 (m, 3H, Ar-H), 8.16 (d, 1H, J=8Hz, Ar-H), 10.27 (s, 1H, OH), 10.67 (s, 1H, NH), 11.54 (s, 1H, NH).
Embodiment 7
Synthetic and the structure of compound GDD-94:N-(2,5-dichloro-4,4-five fluorine propoxy-phenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 4-amidos 2,5-dichloro five fluoropropyl phenylates and 20 milliliter 1, the 2-ethylene dichloride, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 155-157 degree centigrade, yield 49%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.83 (s, 3H, CH
3), 6.61-6.45 (m, 1H, CHF), 7.80 (s, 1H, Ar-H), 8.55 (s, 1H, Ar-H), 11.00 (s, 1H, NH), 11.92 (s, 1H, NH).
Embodiment 8
Synthetic and the structure of compound GDD-96:N-(3, the 4-dichlorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmoles 3,4-dichlorphenamide bulk powder and 20 milliliter 1, the 2-ethylene dichloride is stirred to 3, and the 4-dichlorphenamide bulk powder dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 155-157 degree centigrade, yield 84%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.82 (s, 3H, CH
3), 7.54 (d, 1H, J=8.8Hz, Ar-H), 7.64 (d, 2H, J=8.8Hz, Ar-H), 7.98 (s, 1H, Ar-H), 10.41 (s, 1H, NH), 11.56 (s, 1H, NH).
Embodiment 9
Synthetic and the structure of compound GDD-97:N-(3,5-two chloro-4-hydroxy phenyls)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 4-amidos-2,6-chlorophenesic acid and 20 milliliter 1, the 2-ethylene dichloride is stirred to 4-amido-2, and the 6-chlorophenesic acid is dissolved fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 237-239 degree centigrade, yield 77%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.82 (s, 3H, CH
3), 7.64 (s, 2H, Ar-H), 10.00 (s, 1H, OH), 10.16 (s, 1H, NH), 11.50 (s, 1H, NH).
Embodiment 10
Synthetic and the structure of compound GDD-98:N-(6-amido pyridine-2-yl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmoles 2,6-diamino pyridine and 20 milliliter 1, the 2-ethylene dichloride is stirred to 2, and the 6-diamino pyridine dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 205-207 degree centigrade, yield 90%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.83 (s, 3H, CH
3), 6.21-5.82 (m, 2H, NH
2), 7.43-7.37 (m, 1H, Ar-H), 7.76 (d, 1H, J=8HzAr-H), 7.91-7.87 (m, 1H, Ar-H) 10.63 (s, 1H, NH), 11.71 (s, 1H, NH).
Embodiment 11
Synthetic and the structure of compound GDD-101:N-(2,4-two fluoro-3,5-dichlorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmoles 2,4-two fluoro-3,5-dichlorphenamide bulk powder and 20 milliliter 1, the 2-ethylene dichloride, be stirred to 2,4-two fluoro-3, the 5-dichlorphenamide bulk powder dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 187-189 degree centigrade, yield 92%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.82 (s, 3H, CH
3), 8.25 (s, 1H, Ar-H), 10.56 (s, 1H, NH), 11.92 (s, 1H, NH).
Embodiment 12
Synthetic and the structure of compound GDD-102:N-(4-trifluoromethyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 4-5-trifluoromethylanilines and 20 milliliter 1, the 2-ethylene dichloride, being stirred to the 4-5-trifluoromethylaniline dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 168-170 degree centigrade, yield 92%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.83 (s, 3H, CH
3), 7.73 (s, 2H, Ar-H), 7.79 (s, 2H, Ar-H), 10.52 (s, 1H, NH), 11.58 (s, 1H, NH).
Embodiment 13
Synthetic and the structure of compound GDD-103:N-(4,5-dimethylthiazole-2-yl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 2-amidos-4,5-dimethylthiazole and 20 milliliter 1, the 2-ethylene dichloride is stirred to 2-amido-4, and the 5-dimethylthiazole dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 209-211 degree centigrade, yield 74%; Nuclear magnetic data (DMS0-d6, chemical shift): 2.16 (s, 3H, CH
3), 2.25 (s, 3H, CH
3), 2.81 (s, 3H, CH
3), 11.29 (s, 2H, NH).
Embodiment 14
Synthetic and the structure of compound GDD-104:N-(2-fluoro-4-hydroxy phenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 4-amido-2-fluorophenols and 20 milliliter 1, the 2-ethylene dichloride, being stirred to 4-amido-2-fluorophenol dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 234-236 degree centigrade, yield 83%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.81 (s, 3H, CH
3), 6.72-6,62 (m, 2H, Ar-H), 7.74 (s, 1H, Ar-H), 9.88 (s, 1H, OH), 10.13 (s, 1H, NH), 11.56 (s, 1H, NH).
Embodiment 15
Synthetic and the structure of compound GDD-105:N-(5-ethyl-1,3,4-thiadiazoles-2-yl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 2-amido-5-ethyls-1,3,4-thiadiazoles and 20 milliliter 1, the 2-ethylene dichloride, be stirred to 2-amido-5-ethyl-1,3, the 4-thiadiazoles dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 182-184 degree centigrade, yield 24%; Nuclear magnetic data (DMSO-d6, chemical shift): 1.30 (t, 3H, J=7.4Hz, CH
3), 2.82 (s, 3H, CH
3), 3.00 (q, 2H, J=7.2Hz, CH
2), 11.87 (s, 2H, NH).
Embodiment 16
Synthetic and the structure of compound GDD-106:N-(2-chloro-3,5-two trifluoromethyls)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 2-chloro-3,5-two 5-trifluoromethylanilines and 20 milliliter 1, the 2-ethylene dichloride is stirred to 2-chloro-3, and 5-two 5-trifluoromethylanilines dissolve fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 162-164 degree centigrade, yield 70%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.84 (s, 3H, CH
3), 7.95 (d, 2H, J=1.6Hz, Ar-H), 8.93 (d, 2H, J=1.6Hz, Ar-H), 11.26 (s, 1H, NH), 12.00 (s, 1H, NH).
Embodiment 17
Synthetic and the structure of compound GDD-107:N-(2-nitro 4-aminocarbonyl phenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 3.3 mmole 2-nitros-1,4-phenylenediamine and 20 milliliter 1, the 2-ethylene dichloride is stirred to 2-nitro-1, and the 4-phenylenediamine dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 230-232 degree centigrade, yield 95%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.80 (s, 3H, CH
3), 7.32-7.06 (m, 1H, Ar-H), 7.70 (s, 1H, Ar-H), 8.26-8.03 (m, 1H, Ar-H), 10.46 (s, 1H, NH), 12.01 (s, 1H, NH).
Embodiment 18
Synthetic and the structure of compound GDD-109:N-(8-amido-1-naphthyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 3.3 mmoles 1,8-two amido naphthalenes and 20 milliliter 1, the 2-ethylene dichloride is stirred to 1, and 8-two amido naphthalenes dissolve fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 216-218 degree centigrade, yield 77%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.65 (s, 3H, CH
3), 6.74-6.53 (m, 1H, Ar-H), 7.35-7.09 (m, 2H,, Ar-H), 7.56 (t, 1H, J=8Hz, Ar-H), 7.73 (d, 1H, J=7.6Hz, Ar-H), 7.92 (d, 1H, J=8Hz, Ar-H), 10.51 (s, 1H, NH), 11.60 (s, 1H, NH).
Embodiment 19
Synthetic and the structure of compound GDD-111:N-(2-amido-3-itrile group propionitrile-1-yl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 3.3 mmoles 2,3-two amidos-2-butylene dintrile and 20 milliliter 1, the 2-ethylene dichloride is stirred to 2, and 3-two amidos-2-butylene dintrile dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point 146-148 degree centigrade, yield 47%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.81 (s, 3H, CH
3), 5.36 (s, 2H, NH
2), 9.20 (s, 1H, NH), 11.56 (s, 1H, NH).
Embodiment 20
Synthetic and the structure of compound GDD-115:N-(2-amido-4-aminomethyl phenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 3.3 mmoles 3,4-two amido toluene and 20 milliliter 1, the 2-ethylene dichloride is stirred to 3, and 4-two amido toluene dissolve fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 203-205 degree centigrade, yield 93%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.79 (s, 6H, CH
3), 6.74-6.53 (m, 1H, Ar-H), 7.60-7.58 (m, 2H,, Ar-H), 7.69 (s, 21H, NH), 7.81 (s, 1H, NH), 8.19 (s, 1H, Ar-H), 10.64 (s, 1H, NH), 12.62 (s, 1H, NH).
Embodiment 21
Synthetic and the structure of compound GDD-117:N-(4-amido-6-phenyl-1,3,5-triazines-2-yl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 3.3 mmoles 2,4-two amidos-6-phenyl-1,3,5-triazine and 20 milliliter 1, the 2-ethylene dichloride is stirred to 2,4-two amidos-6-phenyl-1,3,5-triazines dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: greater than 240 degrees centigrade, yield 72%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.80 (s, 3H, CH
3), 7.56-7.47 (m, 3H, Ar-H), 7.70 (s, 1H, Ar-H), 7.82 (s, 1H, Ar-H), 10.65 (s, 1H, NH), 12.62 (s, 1H, NH).
Embodiment 22
Synthetic and the structure of compound GDD-123:N-(2-amido-5-nitrophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 3.3 mmole 4-nitro O-Phenylene Diamines and 20 milliliter 1, the 2-ethylene dichloride, being stirred to 4-nitro O-Phenylene Diamine dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 193-195 degree centigrade, yield 80%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.81 (s, 3H, CH
3), 6.56 (d, 2H, J=8Hz, NH
2), 8.21 (s, 2H, Ar-H), 8.49 (s, 1H, Ar-H), 10.31 (s, 1H, NH), 10.77 (s, 1H, NH).
Embodiment 23
Synthetic and the structure of compound GDD-125:N-(3-amido-4-aminomethyl phenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 3.3 mmoles 2,4-two amido toluene and 20 milliliter 1, the 2-ethylene dichloride is stirred to 2, and 4-two amido toluene dissolve fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 169-171 degree centigrade, yield 50%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.27 (s, 3H, CH
3), 2.84 (s, 3H, CH
3), 6.33-6.31 (m, 1H, NH
2), 6.46 (s, H, NH
2), 6.66-6.63 (m, 1H, Ar-H), 6.95-6.87 (m, 2H, Ar-H), 10.24 (s, 1H, NH), 10.728 (s, 1H, NH).
Embodiment 24
Compound GDD-129:N-[4-(4 '-the amido cyclohexyl methyl) cyclohexyl]-synthesizing of N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea reach the structure evaluation
In 100 milliliters of round-bottomed flasks, add 3.3 mmoles 4,4 '-diamino-dicyclohexyl methane and 20 milliliter 1, the 2-ethylene dichloride is stirred to 4 and dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 186-188 degree centigrade, yield 66%; Nuclear magnetic data (DMSO-d6, chemical shift): 1.922-0.835 (m, 20H, cyclohexyl-H, CH
2), 2.77 (s, 3H, CH
3), 2.78 (s, 2H, CH
2), 3.49 (s, 1H, NH
2), 3.90 (s, 1H, NH
2), 8.11 (s, 1H, NH) 8.85 (s, 1H, NH).
Embodiment 25
Synthetic and the structure of compound GDD-131:N-(4-amido anthraquinonyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 3.3 mmoles 1,4-diamino-anthraquinone and 20 milliliter 1, the 2-ethylene dichloride is stirred to 1, and the 4-diamino-anthraquinone dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 208-210 degree centigrade, yield 54%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.87 (s, 3H, CH
3), 7.79 (s, 2H, Ar-H), 8.23 (s, 1H, Ar-H), 8.54 (s, 2H, Ar-H), 11.65 (s, 1H, NH), 13.01 (s, 1H, NH).
Embodiment 26
Synthetic and the structure of compound GDD-137:N-(2-fluorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 2-fluoroanilines and 20 milliliter 1, the 2-ethylene dichloride, being stirred to the 2-fluoroaniline dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 229-231 degree centigrade, yield 86%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.84 (s, 3H, CH
3), 7.91 (s, 2H, Ar-H), 7.92 (d, 2H, J=7.2Hz, Ar-H), 11.58. (s, 1H, NH), 11.90 (s, 1H, NH).
Embodiment 27
Synthetic and the structure of compound GDD-138:N-(4-phenyl thiazole-2-yl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 2-amido-4-phenyl thiazoles and 20 milliliter 1, the 2-ethylene dichloride, being stirred to 2-amido-4-phenyl thiazole dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 207-209 degree centigrade, yield 89%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.82 (s, 3H, CH
3), 7.09-7.04 (m, 2H, Ar-H), 7.25-7.21 (m, 1H, Ar-H), 7.36-7.31 (m, 1H, Ar-H), 8.14-8.10 (m, 1H, Ar-H), 10.54 (s, 1H, NH), 11.69 (s, 1H, NH).
Embodiment 28
Synthetic and the structure of compound GDD-139:N-(4-(4-chloro-phenyl-) thiazol-2-yl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 2-amido-4-(4-chloro-phenyl-) thiazoles and 20 milliliter 1, the 2-ethylene dichloride, being stirred to 2-amido-4-(4-chloro-phenyl-) thiazole dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 229-231 degree centigrade, yield 89%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.84 (s, 3H, CH
3), 7.49 (d, 2H, J=8.4Hz, Ar-H), 7.79 (s, 1H, Ar-H), 7.94 (d, 2H, J=8.4Hz, Ar-H), 11.57 (s, 1H, NH), 11.90 (s, 1H, NH).
Embodiment 29
Synthetic and the structure of compound GDD-140:N-(5-Trifluoromethyl-1,3,4-thiadiazoles-2-yl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 2-amido-5-Trifluoromethyl-1s, 3,4-thiadiazoles and 20 milliliter 1, the 2-ethylene dichloride, be stirred to 2-amido-5-Trifluoromethyl-1,3, the 4-thiadiazoles dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: greater than 240 degrees centigrade, yield 45%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.78 (s, 3H, CH
3), 8.03 (s, 1H, NH), 8.22 (s, 1H, NH).
Embodiment 30
Synthetic and the structure of compound GDD-141:N-(5-(4-aminomethyl phenyl)-1,3,4-thiadiazoles-2-yl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 2-amido-5-(4-aminomethyl phenyl)-1,3,4-thiadiazoles and 20 milliliter 1, the 2-ethylene dichloride, be stirred to 2-amido-5-(4-aminomethyl phenyl)-1,3, the 4-thiadiazoles dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 146-148 degree centigrade, yield 74%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.27 (s, 3H, CH
3), 2.83 (s, 3H, CH
3), 7.35 (d, 2H, J=8Hz, Ar-H), 7.85 (d, 2H, J=8Hz, Ar-H), 11.74 (s, 1H, NH), 11.93 (s, 1H, NH).
Embodiment 31
Synthetic and the structure of compound GDD-142:N-(2-acidic group phenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 2-amido phenylformic acid and 20 milliliter 1, the 2-ethylene dichloride, being stirred to 2-amido phenylformic acid dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 197-199 degree centigrade, yield 91%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.82 (s, 3H, CH
3), 7.25-7.19 (m, 1H, Ar-H), 7.67-7.59 (m, 1H, Ar-H), 7.98 (d, 1H, J=8Hz, Ar-H), 8.46 (d, 1H, J=8Hz, Ar-H) 11.48 (s, 1H, NH), 12.16 (s, 1H, NH).
Embodiment 32
Synthetic and the structure of compound GDD-143:N-(4-ethoxycarbonyl-1,2,3-thiadiazoles-5-yl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 5-amido-4-group-4 ethyl formates-1,2,3-thiadiazoles and 20 milliliter 1, the 2-ethylene dichloride, be stirred to 5-amido-4-group-4 ethyl formate-1,2, the 3-thiadiazoles dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 152-154 degree centigrade, yield 94%; Nuclear magnetic data (DMSO-d6, chemical shift): 1.42 (t, 3H, J=6.8Hz, CH
3), 2.85 (s, 3H, CH
3), 4,51 (q, 2H, J=7.2Hz, 6.8Hz, CH
3), 12.57 (s, 1H, NH), 12.73 (s, 1H, NH).
Embodiment 33
Synthetic and the structure of compound GDD-145:N-(4-(2,4 dichloro benzene base) thiazol-2-yl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 2-amido-4-(2, the 4-dichlorophenyl) thiazole and 20 milliliter 1, the 2-ethylene dichloride is stirred to 2-amido-4-(2,4 dichloro benzene base) thiazole and dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: greater than 240 degrees centigrade, yield 45%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.82 (s, 3H, CH
3), 7.44 (d, 1H, J=8.4Hz, Ar-H), 7.52 (q, 1H, J=2Hz, 8.4, Ar-H), 7.76 (d, 1H, J=2Hz, Ar-H), 7.95 (s, 1H, Ar-H) 11.40 (s, 1H, NH), 11.85 (s, 1H, NH).
Embodiment 34
Synthetic and the structure of compound GDD-146:N-(6-methoxycarbonyl benzo thiazol-2-yl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 2-amidos-6-methoxycarbonyl benzo thiazole and 20 milliliter 1, the 2-ethylene dichloride, being stirred to 2-amido-6-methoxycarbonyl benzo thiazole dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: greater than 240 degrees centigrade, yield 42%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.85 (s, 3H, CH
3), 2.98 (s, 3H, CH
3), 7.95 (s, 1H, Ar-H), 7.99 (d, 1H, J=8Hz, Ar-H), 8.60 (d, 2H, J=8Hz, Ar-H), 11.84 (s, 1H, NH), 12.10 (s, 1H, NH).
Embodiment 35
Synthetic and the structure of compound GDD-147:N-(4-(4-nitrophenyl) thiazol-2-yl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 2-amido-4-(4-nitrophenyl) thiazoles and 20 milliliter 1, the 2-ethylene dichloride, being stirred to 2-amido-4-(4-nitrophenyl) thiazole dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: greater than 240 degrees centigrade, yield 90%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.85 (s, 3H, CH
3), 8.09 (s, 1H, Ar-H), 8.19 (d, 2H, J=8.8Hz, Ar-H), 8.29 (s, 2H, J=8.8Hz, Ar-H), 11.66 (s, 1H, NH), 11.96 (s, 1H, NH).
Embodiment 36
Synthetic and the structure of compound GDD-148:N-(3-(4-chloro-phenyl-) pyrimidine-4-yl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 2.7 mmole 4-amido-3-(4-chloro-phenyl-) pyrimidines and 20 milliliter 1, the 2-ethylene dichloride, being stirred to 4-amido-3-(4-chloro-phenyl-) pyrimidine dissolves fully, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets solid product, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 142-144 degree centigrade, yield 20%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.75 (s, 3H, CH
3), 7.59 (s, 5H, Ar-H), 8.69 (s, 1H, Ar-H), 9.02 (s, 1H, Ar-H), 10.60 (s, 1H, NH), 11.70 (s, 2H, NH).
Embodiment 37
Compound GDD-54F: the synthetic and structure of adjacent two [N-phenyl-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea] is identified
In 100 milliliters of round-bottomed flasks, add 1.3 mmole O-Phenylene Diamines and 20 milliliter 1, the 2-ethylene dichloride, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester, dropwised in 15 minutes, and produced precipitation immediately, at room temperature stirred 8 hours, after reaction finishes, leave standstill, suction filtration gets the product solid, and the filtrate rotary evaporation removes and desolvates, with volume ratio 1: 3 ethyl acetate: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point 207-210 degree centigrade, yield 51%.Nuclear magnetic data (DMSO-d6, chemical shift): 2.78 (s, 6H, CH
3), 7.28 (q, 2H, J=3.6Hz, 6Hz, Ar-H), 7.73 (q, 2H, J=3.6Hz, 6Hz, Ar-H), 10.29 (s, 2H, NH), 10.23 (s, 2H, NH).
Embodiment 38
Compound GDD-56: the synthetic and structure mirror of two [N-phenyl-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea]
In 100 milliliters of round-bottomed flasks, add 1.3 mmole mphenylenediamines and 20 milliliter 1, the 2-ethylene dichloride, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester, dropwised in 15 minutes, and produced precipitation immediately, at room temperature stirred 8 hours, after reaction finishes, leave standstill, suction filtration gets the product solid, and the filtrate rotary evaporation removes and desolvates, with volume ratio 1: 3 ethyl acetate: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point 192-194 degree centigrade, yield 53%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.83 (s, 6H, CH
3), 7.33 (s, 3H, Ar-H), 7.87 (s, 1H, Ar-H), 10.29 (s, 2H, NH), 11.46 (s, 2H, NH).
Embodiment 39
Compound GDD-58: the synthetic and structure to two-[N-(phenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea] is identified
In 100 milliliters of round-bottomed flasks, add 1.3 mmole Ursol D and 20 milliliter 1, the 2-ethylene dichloride, stir and drip 3 mmole 4-methyl isophthalic acids down, 2,3-thiadiazoles-5-formyl radical isocyanic ester, dropwised in 15 minutes, and produced precipitation immediately, at room temperature stirred 8 hours, after reaction finishes, leave standstill, suction filtration gets solid, and the filtrate rotary evaporation removes and desolvates, with volume ratio 1: 3 ethyl acetate: put into refrigerator behind the sherwood oil recrystallization, separate out solid, combining solid, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point 212-214 degree centigrade, yield 48%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.89 (s.6H, CH
3), 7.62-7.76 (m, 4H, Ar-H), 10.31 (s, 2H, NH), 11.53 (s, 1H, NH).Fusing point 212-214 degree centigrade, yield 48%.
Embodiment 40
Synthetic and the structure of compound GDD-99:N-(pyridine-2,6-two bases)-N '-two (4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 1.3 mmoles 2,6-diamino pyridine and 20 milliliter 1, the 2-ethylene dichloride is stirred to 2, the 6-diamino pyridine dissolves fully, with 2, the drips of solution of 6-diamino pyridine is added to 3 mmole 4-methyl isophthalic acids under stirring, and 2, in 3-thiadiazoles-5-formyl radical isocyanic ester, dropwised in 15 minutes, and produced precipitation immediately, at room temperature stirred 8 hours, after reaction finishes, leave standstill, suction filtration gets the product solid, and the filtrate rotary evaporation removes and desolvates, with volume ratio 1: 3 ethyl acetate: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: greater than 240 degrees centigrade, yield 68%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.85 (s, 6H, CH
3), 7.80 (s, 1H, Ar-H), 7.82 (s, 1H, Ar-H), 7.95 (m, 1H, Ar-H), 10.69 (s, 2H, NH), 11.68 (s, 2H, NH).
Embodiment 41
Synthetic and the structure of compound GDD-108:N-(2-nitrophenyl-1,4-two bases)-N '-two (4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 1.3 mmole 2-nitros-1,4-phenylenediamine and 20 milliliter 1, the 2-ethylene dichloride, be stirred to 2-nitro-1, the 4-phenylenediamine dissolves fully, with 2-nitro-1, the drips of solution of 4-phenylenediamine is added to 3 mmole 4-methyl isophthalic acids under stirring, and 2,3-thiadiazoles-5-formyl radical isocyanic ester, dropwised in 15 minutes, and produced precipitation immediately, at room temperature stirred 8 hours, reaction finishes, leave standstill, suction filtration gets the product solid, and the filtrate rotary evaporation removes and desolvates, with volume ratio 1: 3 ethyl acetate: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 212-214 degree centigrade, yield 87%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.83 (s, 6H, CH
3), 7.92-7.86 (m, 1H, Ar-H), 8.40 (d, 1H, J=9.2Hz, Ar-H), 8.60 (d, 1H, J=2.8Hz, Ar-H), 10.49 (s, 1H, NH), 11.59 (s, 1H, NH), 11.76 (s, 1H, NH), 11.79 (s, 1H, NH).
Embodiment 42
Synthetic and the structure of compound GDD-110:N-(naphthyl-1,8-two bases)-N '-two (4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 1.3 mmoles 1,8-two amido naphthalenes and 20 milliliter 1, the 2-ethylene dichloride is stirred to 1,8-two amido naphthalenes dissolve fully, with 1, the drips of solution of 8-two amido naphthalenes is added to 3 mmole 4-methyl isophthalic acids under stirring, and 2,3-thiadiazoles-5-formyl radical isocyanic ester, dropwised in 15 minutes, and produced precipitation immediately, at room temperature stirred 8 hours, after reaction finishes, leave standstill, suction filtration gets the product solid, and the filtrate rotary evaporation removes and desolvates, with volume ratio 1: 3 ethyl acetate: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 211-213 degree centigrade, yield 93%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.65 (s, 6H, CH
3), 7.59-7.55 (m, 2H, Ar-H), 7.72 (d, 2H,, J=7.2Hz, Ar-H), 7.93 (d, 2H, J=7.2Hz, Ar-H), 10.5 (s, 2H, NH), 11.59 (s, 2H, NH).
Embodiment 43
Synthetic and the structure of compound GDD-112:N-(2-cyano group vinyl cyanide-1,1-two bases)-N '-two (4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 1.3 mmoles 3,3-two amidos-2-butylene dintrile and 20 milliliter 1, the 2-ethylene dichloride, be stirred to 3,3-two amidos-2-butylene dintrile dissolves fully, with 3, the drips of solution of 3-two amidos-2-butylene dintrile is added to 3 mmole 4-methyl isophthalic acids under stirring, and 2,3-thiadiazoles-5-formyl radical isocyanic ester, dropwised in 15 minutes, and produced precipitation immediately, at room temperature stirred 8 hours, after reaction finishes, leave standstill, suction filtration gets the product solid, and the filtrate rotary evaporation removes and desolvates, with volume ratio 1: 3 ethyl acetate: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 157-159 degree centigrade, yield 70%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.84 (s, 6H, CH
3), 10.13 (s, 1H, NH), 10.52 (s, 1H, NH), 11.46 (s, 1H, NH), 11.79 (s, 1H, NH).
Embodiment 44
Synthetic and the structure of compound GDD-116:N-(4-methylbenzene-3,4-two bases)-N '-two (4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 1.3 mmoles 3,4-two amido toluene and 20 milliliter 1, the 2-ethylene dichloride is stirred to 3,4-two amido toluene dissolve fully, with 3, the drips of solution of 4-two amido toluene is added to 3 mmole 4-methyl isophthalic acids under stirring, and 2,3-thiadiazoles-5-formyl radical isocyanic ester, dropwised in 15 minutes, and produced precipitation immediately, at room temperature stirred 8 hours, after reaction finishes, leave standstill, suction filtration gets the product solid, and the filtrate rotary evaporation removes and desolvates, with volume ratio 1: 3 ethyl acetate: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 181-183 degree centigrade, yield 83%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.80 (s, 9H, CH
3), 7.72-7.70 (m, 2H, Ar-H), 8.04 (s, 1H, Ar-H), 10.64 (s, 2H, NH), 12.61 (s, 2H, NH).
Embodiment 45
Synthetic and the structure of compound GDD-118:N-(4-phenyl-1,3,5-triazines-2,6-two bases)-N '-two (4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 1.3 mmoles 2,4-two amidos-6-phenyl-1,3,5-triazine and 20 milliliter 1, the 2-ethylene dichloride is stirred to 2,4-two amidos-6-phenyl-1,3, the 5-triazine is dissolved fully, stirs down 2,4-two amidos-6-phenyl-1,3, the drips of solution of 5-triazine is added to 3 mmole 4-methyl isophthalic acids, 2,3-thiadiazoles-5-formyl radical isocyanic ester, dropwised in 15 minutes, and produced precipitation immediately, at room temperature stirred 8 hours, after reaction finishes, leave standstill, suction filtration gets the product solid, and the filtrate rotary evaporation removes and desolvates, with volume ratio 1: 3 ethyl acetate: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 199-201 degree centigrade, yield 58%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.76 (s, 3H, CH
3), 2.77 (s, 3H, CH
3), 7.08-7.05 (m, 1H, Ar-H), 7.28-7.16 (m, 2H, Ar-H), 7.59-7.53 (m, 2H, Ar-H), 10.08 (s, 1H, NH), 10.21 (s, 1H, NH), 10.44 (s, 1H, NH), 10.60 (s, 1H, NH).
Embodiment 46
Synthetic and the structure of compound GDD-120:N-(hexamethylene-1,2-two bases)-N '-two (4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 1.3 mmoles 1,2-diamines basic ring hexane and 20 milliliter 1, the 2-ethylene dichloride, with 1, the drips of solution of 2-diamines basic ring hexane is added to 3 mmole 4-methyl isophthalic acids under stirring, and 2,3-thiadiazoles-5-formyl radical isocyanic ester, dropwised in 15 minutes, and produced precipitation immediately, at room temperature stirred 8 hours, after reaction finishes, leave standstill, suction filtration gets the product solid, and the filtrate rotary evaporation removes and desolvates, with volume ratio 1: 3 ethyl acetate: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 202-204 degree centigrade, yield 85%; Nuclear magnetic data (DMSO-d6, chemical shift): 1.51-1.19 (m, 10H, cyclohexyl-H), 2.76 (s, 6H, CH
3), 11.24 (s, 2H, NH).
Embodiment 47
Synthetic and the structure of compound GDD-124:N-(4-oil of mirbane-1,2-two bases)-N '-two (4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 1.3 mmole 4-nitro O-Phenylene Diamines and 20 milliliter 1, the 2-ethylene dichloride, being stirred to 4-nitro O-Phenylene Diamine dissolves fully, drips of solution with 4-nitro O-Phenylene Diamine under stirring is added to 3 mmole 4-methyl isophthalic acids, 2,3-thiadiazoles-5-formyl radical isocyanic ester dropwised in 15 minutes, produce precipitation immediately, at room temperature stirred 8 hours, and after reaction finishes, left standstill, suction filtration gets the product solid, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 204-206 degree centigrade, yield 93%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.79 (s, 3H, CH
3), 2.80 (s, 3H, CH
3), 8.21 (m, 2H, Ar-H), 8.48 (s, 1H, Ar-H), 10.31 (s, 1H, NH), 10.77 (s, 1H, NH), 11.81 (s, 1H, NH), 11.88 (s, 1H, NH).
Embodiment 48
Synthetic and the structure of compound GDD-126:N-(4-methylbenzene-1,3-two bases)-N '-two (4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 1.3 mmoles 2,4-two amido toluene and 20 milliliter 1, the 2-ethylene dichloride is stirred to 2,4-two amido toluene dissolve fully, with 2, the drips of solution of 4-two amido toluene is added to 3 mmole 4-methyl isophthalic acids under stirring, and 2,3-thiadiazoles-5-formyl radical isocyanic ester, dropwised in 15 minutes, and produced precipitation immediately, at room temperature stirred 8 hours, after reaction finishes, leave standstill, suction filtration gets the product solid, and the filtrate rotary evaporation removes and desolvates, with volume ratio 1: 3 ethyl acetate: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 227-229 degree centigrade, yield 92%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.27 (s, 3H, CH
3), 2.83 (s, 6H, CH
3), 7.27-7.23 (m, 1H, Ar-H), 7.36-7.34 (m, 1H, Ar-H), 8.16 (s, 1H, Ar-H), 10.21 (s, 1H, NH), 10.28 (s, 1H, NH), 11.40 (s, 1H, NH), 11.62 (s, 1H, NH).
Embodiment 49
Synthetic and the structure of compound GDD-130:N-(dicyclohexyl methylene radical-4,4 '-two bases)-N '-two (4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 1.3 mmoles 4,4 '-diamino-dicyclohexyl methane and 20 milliliter 1, the 2-ethylene dichloride, be stirred to 4,4 '-diamino-dicyclohexyl methane dissolves fully, drips of solution with 4 under stirring is added to 3 mmole 4-methyl isophthalic acids, 2,3-thiadiazoles-5-formyl radical isocyanic ester, dropwised in 15 minutes, and produced precipitation immediately, at room temperature stirred 8 hours, after reaction finishes, leave standstill, suction filtration gets the product solid, and the filtrate rotary evaporation removes and desolvates, with volume ratio 1: 3 ethyl acetate: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 238-240 degree centigrade, yield 70%; Nuclear magnetic data (DMSO-d6, chemical shift): 1.93-0.91 (m, 20H, cyclohexyl-H, CH
2), 2.77 (s, 3H, CH
3), 2.78 (s, 3H, CH
3), 2.79 (s, 2H, CH
2), 8.22 (s, 1H, NH) 8.39 (s, 1H, NH), 11.13 (s, 1H, NH) 11.62 (s, 1H, NH).
Embodiment 50
Synthetic and the structure of compound GDD-132:N-(anthraquinone-1,4-two bases)-N '-two (4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea is identified
In 100 milliliters of round-bottomed flasks, add 1.3 mmoles 1,4-diamino-anthraquinone and 20 milliliter 1, the 2-ethylene dichloride is stirred to 1, the 4-diamino-anthraquinone dissolves fully, with 1, the drips of solution of 4-diamino-anthraquinone is added to 3 mmole 4-methyl isophthalic acids under stirring, and 2,3-thiadiazoles-5-formyl radical isocyanic ester, dropwised in 15 minutes, and produced precipitation immediately, at room temperature stirred 8 hours, after reaction finishes, leave standstill, suction filtration gets the product solid, and the filtrate rotary evaporation removes and desolvates, with volume ratio 1: 3 ethyl acetate: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 226-228 degree centigrade, yield 40%; Nuclear magnetic data (DMSO-d6, chemical shift): 2.88 (s, 6H, CH
3), 7.95-7.92 (m, 2H, Ar-H), 8.24-8.19 (m, 1H, Ar-H), 8.82 (s, 2H, Ar-H), 11.66 (s, 2H, NH), 13.10 (s, 1H, NH).
Embodiment 51
Compound GDD-136:N-(4,4-dimethyl cyclohexane-1-base-3-methylene radical-)-synthesizing of N '-two (4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical) urea reach the structure evaluation
In 100 milliliters of round-bottomed flasks, add 1.3 mmole 1-amino-3-amino methyls-3,3,5-trimethyl-cyclohexane and 20 milliliter 1, the 2-ethylene dichloride, stir down 1-amino-3-amino methyl-3,3, the 5-trimethyl-cyclohexane is added drop-wise to 3 mmole 4-methyl isophthalic acids, 2,3-thiadiazoles-5-formyl radical isocyanic ester, dropwised in 15 minutes, and produced precipitation immediately, at room temperature stirred 8 hours, after reaction finishes, leave standstill, suction filtration gets the product solid, and the filtrate rotary evaporation removes and desolvates, with volume ratio 1: 3 ethyl acetate: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; Fusing point: 152-154 degree centigrade, yield 38%; Nuclear magnetic data (DMSO-d6, chemical shift): 0.94 (s, 4H, C
2H
4), 1.06 (s, 6H, 2CH
3), 1.15-1.08 (m, 3H, CH
2, CH), and 1.25-1.22 (m, 1H, CH), 2.76 (s, 3H, CH
3), 2.78 (s, 3H, CH
3), 3.09-2.99 (s, 2H, CH
2), 8.06 (s, 1H, NH), 8.28 (s, 1H, NH), 11.17 (s, 2H, NH).
Adopt synthetic other pairs of method (4-replacement-1 of present embodiment, 2,3-thiadiazoles-5-formyl urea) compounds has same effect, only need change the diamines in the present embodiment into 2, the 3-diamino-pyridine, 2, the 4-diamino-pyridine, 2, the 5-diamino-pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 3, the 5-diamino-pyridine, 2,3-diamino thiophene, 2,4-diamino thiophene, 2,5-diamino thiophene, 3,4-diamino thiophene, 2,3-diamino furans, 2,4-diamino furans, 2,5-diamino furans, 3,4-diamino furans, 3,4-diaminostilbene, 2, the 5-oxadiazole, 2,3-diamino-5,6-dicyano pyrazine, 2,3-diamino-aromatic diamines or heteroaromatic diamines such as 5-bromo-pyrazine.
Embodiment 52
High reactivity 4-of the present invention replaces-1,2, the insecticidal activity of 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII:
Synthetic new compound of the present invention sees Table 3 to the measurement result of small cabbage moth and mosquito larvae insecticidal activity, table 3 shows, GDD-52, GDD-91F, GDD-94, GDD-97, GDD-101, GDD-102, GDD-103, GDD-106, GDD-117, GDD-143 and GDD-99, GDD-108, GDD-116, GDD-124, GDD-126, GDD-136 under 400mg/L concentration to the insecticidal activity of small cabbage moth significantly greater than corresponding contrast medicament 12.5% of the young urea that goes out.GDD-52, GDD-91F, GDD-94, GDD-96, GDD-97, GDD-98, GDD-101, GDD-102, GDD-104, GDD-106, GDD-125, GDD-147 and GDD-99, GDD-108, GDD-112, GDD-120, GDD-136 under 5mg/L concentration to the insecticidal activity of mosquito larvae significantly greater than corresponding contrast medicament go out young urea 40% or quite active with it.Therefore, this compounds has shown that good desinsection is alive.
Embodiment 53
High reactivity 4-of the present invention replaces-1,2, the antibacterial or fungicidal activity of 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII:
The title and the code name of the frequently seen plants pathogenic fungi of the present invention's test comprise AS: tomato early blight bacterium (Alternaria solani); BC: botrytis cinerea pers (Botrytis cinerea); CA: peanut Cercospora bacteria (Cercospora arachidicola); GZ: fusarium graminearum (Gibberella zeae); PI: phytophthora infestans (Phytophthora infestans (Mont.) deBary); PP: ring rot of apple bacterium (Physalospora piricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); RC: cereal rhizoctonia (Rhizoctonia cerealis); SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum), these bacterial classifications have good representativeness, can represent the kind of most of pathogenic bacteria that the field takes place in the agriculture production.Thalli growth rate method measurement result sees Table 3, table 3 shows, when 50 mcg/ml, all new compounds of synthetic of the present invention go out the fungicidal activity of young urea to AS except GDD-52, GDD-54F, GDD-136, GDD-101, GDD-104, GDD-147 are lower than the contrast medicament to the fungicidal activity of AS, and the fungicidal activity of all the other compounds is significantly higher than contrast medicament 5% the fungicidal activity of young urea to AS that go out; Except that compound GDD-56, all new compounds are significantly higher than contrast medicament 11% the fungicidal activity of young urea to BC that go out to the fungicidal activity of BC; GDD-91F, GDD-93, GDD-94, GDD-96, GDD-97, GDD-101, GDD-102, GDD-103, GDD-106, GDD-111, GDD-115, GDD-117, GDD-123, GDD-131, GDD-137, GDD-138, GDD-143, GDD-145, GDD-147, GDD-148 and GDD-58, GDD-118, GDD-126, GDD-132 are significantly higher than contrast medicament 7% the fungicidal activity of young urea to CA that go out to the fungicidal activity of CA; Except that compound GDD-56, all new compounds of synthetic of the present invention all have in various degree fungicidal activity to GZ, and the contrast medicament young urea that goes out does not have fungicidal activity to GZ; GDD-91F, GDD-97, GDD-123, GDD-131, GDD-139, GDD-140 and GDD-54F, GDD-58, GDD-120, GDD-132, GDD-147 are significantly higher than contrast medicament 8% the fungicidal activity of young urea to PI that go out to the fungicidal activity of PI; All new compounds of synthetic of the present invention all have in various degree fungicidal activity to PP, and the contrast medicament young urea that goes out does not almost have fungicidal activity to PP; Except that compound GDD-99 and GDD-112, all new compounds of synthetic of the present invention all have in various degree fungicidal activity to PS, and the contrast medicament young urea that goes out does not almost have fungicidal activity to PS; All new compounds of synthetic of the present invention all are higher than contrast medicament 22% the fungicidal activity of young urea to RC that go out to the fungicidal activity of RC; All new compounds go out the young urea except GDD-94, GDD-96, GDD-102, GDD-103 and GDD-54F, GDD-58, GDD-108, GDD-126 are lower than the contrast medicament to the fungicidal activity of SS, and the fungicidal activity of all the other compounds is significantly higher than contrast medicament 14% the fungicidal activity of young urea to SS that go out; Therefore, this compounds has shown excellent bactericidal activity.
Embodiment 54
High reactivity 4-of the present invention replaces-1,2, the antiviral activity of 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII:
Bioassay results shows, the most of high reactivity 4-of synthetic of the present invention replaces-1,2,3-thiadiazole formoxyl ureide compound and two (4-replacement-1,2,3-thiadiazoles-5-formyl urea) compounds has good activity of resisting tobacco mosaic virus, and the withered spot method of half leaf of all compounds is measured activity all less than 30%, but the inactivate activity of all compounds is all more than 65%, and the inactivate activity of corresponding control compound Ningnanmycin is 50%; The therapeutic activity of compound of the present invention is also below 30%, all new compounds are lower than the contrast medicament tiadinil except the activity of GDD-93, GDD-98, GDD-111, GDD-129 and GDD-120, GDD-130, the anti-TMV of GDD-136 evoking tobacco, the activity of the anti-TMV of all the other compound evoking tobaccos is significantly higher than the induced activity of contrast medicament tiadinil 45% all more than 60%.Up till now, the compound of not seeing homogeneous structure is to the inactivate activity of TMV and the activity report of the anti-TMV of evoking tobacco, and the present invention has found the antiviral activity of this compounds first.Can know from the basic principles of chemistry, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-benzoyl urea compound and two (4-replacement-1,2,3-thiadiazoles-5-formyl urea) thus compounds can produce the 4-methyl isophthalic acid from carbonyl fracture in plant with after the water molecules effect, 2,3-thiadiazoles-5-formic acid, confirm also that by relevant software prediction and test compound of the present invention can produce 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid in the degraded of plant materials intracellular metabolite, bibliographical information confirms the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid has the resistance of inducing plant generation to the phytopathy original, can be used in the control of Plant diseases and viral diseases of plants, therefore, compound of the present invention can be used in Antiphytoviral medicament or inducing plant Antiphytoviral medicaments preparation.
Embodiment 55
High reactivity 4-of the present invention replaces-1,2, the application in 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII and sterilant combination control agricultural and forestry and the gardening plant insect pest
High reactivity 4-of the present invention replaces-1,2,3-thiadiazole formoxyl ureide compound V and high reactivity are two, and (4-replaces-1,2,3-thiadiazoles-5-formyl urea) the total quality percentage composition of compounds VII in composition is 1%-90%, and high reactivity 4-of the present invention replaces-1,2, the ratio of 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII and commercially available agricultural chemical is mass percent 1%: 99% to 99%: 1%; 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, the dispersible body preparation, the dispersible solid preparation, 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, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, the capsule granula, capsule suspension, can disperse dense dose, pulvis, dry mixing kind pulvis, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the seed treatment suspension agent, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, big granula, the drift pulvis, granula, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix and adorn agent, the medicine lacquer, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, plant the clothing agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, soluble powder, the seed treatment water solube powder, the ultra-low volume suspension agent, tablet, follow the trail of pulvis, ultra low volume liquids, the steam releasing agent, water-dispersible granules, wettable powder, in the wet-mixing kind water-dispersible powder 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; High reactivity 4-of the present invention replaces-1,2,3-thiadiazole formoxyl ureide compound or two (4-replacement-1,2,3-thiadiazoles-5-formyl urea) compounds 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, Bistrfluron, 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 prevention effect of composition is good, and drug effect is played stably.
The crop that these compositions are suitable for comprises paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, 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, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape.
Embodiment 56
High reactivity 4-of the present invention replaces-1,2, the application in 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII and sterilant combination control agricultural and forestry and the gardening plant disease
；4--1；2；3-V （4--1；2；3--5-）VII；；；；4--1；2；3--5-；4--1；2；3--5-；4--1；2，3--5-；DL-β-； （isotianil）；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；。 High reactivity 4-of the present invention replaces-1,2,3-thiadiazole formoxyl ureide compound V and high reactivity are two, and (4-replaces-1,2,3-thiadiazoles-5-formyl urea) the total quality percentage composition of compounds VII in composition is 1%-90%, and high reactivity 4-of the present invention replaces-1,2, the ratio of 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII and commercially available agricultural chemical is mass percent 1%: 99% to 99%: 1%; The prevention effect of medicament is good, and these compositions have certain synergism and summation action, does 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 surplus the Achyla, Aphanomyces, pythium, phytophthora, Sclerospora, Plasmopara, false Peronospora, Peronospora of Oomycete etc. 20 and to belong to the disease that produces, as other diseases of plurality of cereals crop, cash crop, gardening plant and forestry plants such as seedling blight of rice, tomato root rot, the late blight of potato, black shank, millet Powdery Mildew, downy mildew of garpe, downy mildew of lettuce, cucumber downy mildew, cucumber anthracnose etc.; The formulation of composition processing is selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, 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, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, the capsule granula, capsule suspension, can disperse dense dose, pulvis, dry mixing kind pulvis, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the seed treatment suspension agent, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, big granula, the drift pulvis, granula, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix and adorn agent, the medicine lacquer, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, plant the clothing agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, soluble powder, the seed treatment water solube powder, the ultra-low volume suspension agent, tablet, follow the trail of pulvis, ultra low volume liquids, the steam releasing agent, water-dispersible granules, wettable powder, in the wet-mixing kind water-dispersible powder any one.
The crop that these compositions are suitable for comprises that cereal (comprises paddy, wheat, barley, oat, corn, millet, Chinese sorghum etc.), tuber crops (comprise sweet potato, potato, cassava etc.), beans (comprises soybean, broad bean, pea, mung bean, red bean etc.) and fiber (cotton, crudefiber crop, silkworm and mulberry etc.), oil plant (peanut, rape, sesame, soybean, Sunflower Receptacle etc.), sugar material (beet, sugarcane etc.), beverage (tealeaves, coffee, cocoa etc.), hobby (tobacco leaf etc.), medicinal (genseng, the bulb of fritillary etc.), the torrid zone (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.
Embodiment 57
High reactivity 4-of the present invention replaces-1,2, and 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII and antiviral agent are combined in the application in control agricultural and forestry and the gardening plant virus disease
High reactivity 4-replaces-1,2,3-thiadiazole formoxyl ureide compound V and high reactivity are two, and (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII and existing Antiphytoviral medicament diazosulfide, tiadinil (TDL), different metsulfovax (isotianil), 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, allyl isothiazole, well ridge azanol, any 1 or 2 compound combinations in the jingganmycin; Be used to prevent and treat the agricultural plants virus disease, these virus diseases are selected from 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, any in cotton virus disease and the various fruit tree virus disease, wherein endanger serious being selected from: 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, any in the cybidium ring spot virus.The crop that these compositions are suitable for is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, 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, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, agriculturals such as potted landscape, gardening, economical, plants such as forestry; The use of these compositions makes the immunizing power of crop self be improved, and has induced the control of plant generation to viral diseases of plants when producing the control of insect especially infection insect; Also can produce the direct prevention effect of virus disease; Therefore, these compositions can be used for Antiphytoviral medicament and inducing plant Antiphytoviral medicaments preparation and purposes.High reactivity 4-of the present invention replaces-1,2,3-thiadiazole formoxyl ureide compound V and high reactivity are two, and (4-replaces-1,2,3-thiadiazoles-5-formyl urea) the total quality percentage composition of compounds VII in composition is 1%-90%, and high reactivity 4-of the present invention replaces-1,2, the ratio of 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII and commercially available agricultural chemical is mass percent 1%: 99% to 99%: 1%; The formulation of composition processing is selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, 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, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, the capsule granula, capsule suspension, can disperse dense dose, pulvis, dry mixing kind pulvis, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the seed treatment suspension agent, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, big granula, the drift pulvis, granula, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix and adorn agent, the medicine lacquer, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, plant the clothing agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, soluble powder, the seed treatment water solube powder, the ultra-low volume suspension agent, tablet, follow the trail of pulvis, ultra low volume liquids, the steam releasing agent, water-dispersible granules, wettable powder, in the wet-mixing kind water-dispersible powder any one; All show addition or synergism between these compositions, when keeping insecticidal activity, the effect that its antiviral activity all uses separately greater than any one compound; Find no the composition of antagonistic action, the drug effect lasting period of composition is long.
From the basic principles of chemistry as can be known, the 4-methyl isophthalic acid, 2, thereby 3-thiadiazoles-5-benzoyl urea compound can produce the 4-methyl isophthalic acid from the carbonyl fracture in plant with after the water molecules effect, 2,3-thiadiazoles-5-formic acid, confirm also that by relevant software prediction and test compound of the present invention can produce the 4-methyl isophthalic acid in the degraded of plant materials intracellular metabolite, 2,3-thiadiazoles-5-formic acid, bibliographical information confirms 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid has the resistance of inducing plant generation to the phytopathy original, can be used in the control of Plant diseases and viral diseases of plants.Therefore, these compositions can be used in preparation Antiphytoviral medicament and inducing plant Antiphytoviral medicament.
Meanwhile, this compounds also has insecticidal activity, can be used to prevent and treat Agricultural pests such as Asiatic migrotory locust simultaneously, 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 the harm that must post insect pests such as fly.
Embodiment 58
High reactivity 4-of the present invention replaces-1,2, the complete processing and the stability of 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII and commercially available agricultural chemical compound preparation
High reactivity 4-of the present invention replaces-1,2,3-thiadiazole formoxyl ureide compound V and high reactivity are two, and (4-replaces-1,2,3-thiadiazoles-5-formyl urea) the mixed preparation complete processing of compounds VII and commercially available agricultural chemical sees Table 4, table 4 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, 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, the cold storage test of process preparation, 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 composition effective constituent in 5%, the composite preparation qualified stability.
Table 1 high reactivity 4-of the present invention replaces-1,2, chemical structure and the physical and chemical parameter of 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII
Table 1 high reactivity 4-of the present invention replaces-1,2, chemical structure and the physical and chemical parameter (continuing) of 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII
Table 1 high reactivity 4-of the present invention replaces-1,2, chemical structure and the physical and chemical parameter (continuing) of 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII
Other high reactivities of table 2 synthetic of the present invention 4-replaces-1,2, the chemical structure of 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII
Table 3 synthetic high reactivity of the present invention 4-replaces-1,2, the desinsection of 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII, fungicidal activity (/ %)
| Compound | AS | BC | CA | GZ | PI | PP | PS | RC | SS | 200mg/L* | 400mg/L* | 5mg/L# |
| GDD-52 | 10 | 14 | 0 | 0 | 16 | 26 | 0 | 0 | 14 | 43.70 | 100 | 100 |
| GDD-91F | 20.00 | 26.92 | 26.32 | 3.13 | 25.93 | 40.00 | 17.11 | 40.00 | 58.06 | ND | 25 | 10 |
| GDD-92 | 10.00 | 50.00 | 15.79 | 0 | 14.81 | 42.50 | 32.89 | 55.00 | 35.48 | ND | 12.8 | 20 |
| GDD-93 | 35.00 | 53.85 | 36.84 | 6.25 | 11.11 | 45.00 | 10.53 | 55.00 | 70.97 | ND | 15 | 10 |
| GDD-94 | 10.00 | 42.31 | 26.32 | 18.75 | 7.41 | 30.00 | 5.26 | 50.00 | 9.68 | ND | 75 | 100 |
| GDD-96 | 15.00 | 23.08 | 26.32 | 12.50 | 3.70 | 35.00 | 0 | 45.00 | 3.23 | ND | 7.7 | 60 |
| GDD-97 | 10.00 | 38.46 | 26.32 | 3.13 | 22.22 | 45.00 | 5.26 | 40.00 | 80.65 | ND | 19 | 20 |
| GDD-98 | 33.33 | 18.42 | 9.09 | 37.50 | 0 | 31.67 | 4.76 | 50.00 | 70.21 | ND | 5 | 60 |
| GDD-101 | 4.17 | 23.68 | 22.73 | 12.50 | 18.42 | 10.00 | 2.38 | 33.33 | 59.57 | ND | 97.5 | 100 |
| GDD-102 | 16.67 | 42.11 | 27.27 | 41.07 | 7.89 | 26.67 | 21.43 | 47.22 | 6.38 | ND | 27.5 | 100 |
| GDD-103 | 37.50 | 0 | 22.73 | 30.36 | 10.53 | 23.33 | 7.14 | 44.44 | 2.13 | ND | 21 | 50 |
| GDD-104 | 8.33 | 15.79 | 13.64 | 8.93 | 2.63 | 8.33 | 3.57 | 25.00 | 57.45 | ND | 5 | 100 |
| GDD-105 | 12.50 | 15.79 | 18.18 | 32.14 | 0 | 15.00 | 5.95 | 38.89 | 74.47 | ND | 17 | 50 |
| GDD-106 | 16.67 | 28.95 | 50.00 | 67.86 | 10.53 | 66.67 | 42.86 | 76.39 | 57.45 | ND | 100 | 100 |
| GDD-107 | 20.83 | 18.42 | 13.64 | 32.14 | 2.63 | 40.00 | 4.76 | 52.78 | 65.96 | ND | 13 | 20 |
| GDD-109 | 54.17 | 21.05 | 9.09 | 37.50 | 7.89 | 46.67 | 47.62 | 63.89 | 61.70 | ND | 0 | 20 |
| GDD-111 | 33.33 | 55.26 | 36.36 | 55.36 | 5.26 | 43.33 | 57.14 | 52.78 | 91.49 | ND | 3.85 | |
| GDD-115 | 46.15 | 43.33 | 23.08 | 50.00 | 13.64 | 40.91 | 60.98 | 59.18 | 56.25 | ND | 10 | 10 |
| GDD-117 | 30.77 | 46.67 | 23.08 | 19.23 | 13.64 | 36.36 | 58.54 | 55.10 | 18.75 | ND | 20 | 40 |
| GDD-123 | 38.46 | 46.67 | 30.77 | 23.08 | 22.73 | 18.18 | 48.78 | 59.18 | 56.25 | ND | 5 | 30 |
| GDD-125 | 23.08 | 40.00 | 15.38 | 11.54 | 13.64 | 45.45 | 46.34 | 55.10 | 31.25 | ND | 0 | 100 |
| GDD-129 | 23.08 | 46.67 | 15.38 | 11.54 | 9.09 | 45.45 | 46.34 | 53.06 | 50.00 | ND | 7 | 10 |
| GDD-131 | 38.46 | 50.00 | 23.08 | 15.38 | 31.82 | 54.55 | 78.05 | 57.14 | 50.00 | ND | 0 | 30 |
| GDD-137 | 23.08 | 46.67 | 30.77 | 26.92 | 13.64 | 50.00 | 39.02 | 57.14 | 50.00 | ND | 2.6 | 10 |
| GDD-138 | 38.46 | 43.33 | 23.08 | 23.08 | 9.09 | 31.82 | 53.66 | 55.10 | 62.50 | ND | 5 | 40 |
| GDD-139 | 20.00 | 40.74 | 17.39 | 20.00 | 48.57 | 39.58 | 66.67 | 70.77 | 57.14 | ND | 15 | 40 |
| GDD-140 | 20.00 | 51.85 | 13.04 | 24.00 | 20.00 | 45.83 | 61.90 | 73.85 | 57.14 | ND | 18 | 10 |
| GDD-141 | 10.00 | 50.00 | 17.39 | 16.00 | 11.43 | 12.50 | 54.76 | 63.08 | 57.14 | ND | 5 | 20 |
| GDD-142 | 16.67 | 50.00 | 17.39 | 22.00 | 14.29 | 31.25 | 66.67 | 64.62 | 57.14 | ND | 5 | 20 |
| GDD-143 | 30.00 | 51.85 | 21.74 | 30.00 | 17.14 | 41.67 | 47.62 | 73.85 | 42.86 | ND | 35 | 30 |
| GDD-145 | 16.67 | 50.00 | 26.09 | 16.00 | 11.43 | 43.75 | 47.62 | 61.54 | 42.86 | ND | 15 | 10 |
| GDD-146 | 33.33 | 53.70 | 4.35 | 18.00 | 17.14 | 37.50 | 46.43 | 56.92 | 42.86 | ND | 10 | 30 |
| GDD-147 | 22.73 | 18.52 | 41.18 | 31.03 | 16.67 | 28.57 | 52.17 | 55.56 | 52.50 | ND | 16 | 60 |
| GDD-148 | 23.33 | 48.15 | 13.04 | 26.00 | 14.29 | 31.25 | 58.33 | 63.08 | 57.14 | ND | 10 | 10 |
| GDD-54 | 9.52 | 18.18 | 0 | 33.33 | 19.05 | 58.97 | 21.13 | 38.71 | 0 | ND | 0 | - |
| GDD-56 | 23.81 | 4.55 | 0 | 0 | 0 | 33.33 | 38.03 | 9.68 | 54.55 | 3 | ND | 20 |
| GDD-58 | 23.81 | 27.27 | 14.29 | 33.33 | 23.81 | 71.79 | 14.08 | 48.39 | 0 | ND | ND | ND |
| GDD-99 | 25 | 15.79 | 9.09 | 48.21 | 0 | 38.33 | 7.14 | 50 | 48.94 | - | 25 | 60 |
| GDD-108 | 16.67 | 15.79 | 9.09 | 44.64 | 2.63 | 43.33 | 10.71 | 47.22 | 2.13 | - | 18 | 70 |
| GDD-110 | 16.67 | 21.05 | 4.55 | 42.86 | 7.89 | 38.33 | 16.67 | 55.56 | 78.72 | - | 10.99 | 30 |
| GDD-112 | 20.83 | 28.95 | 0 | 53.57 | 5.26 | 41.67 | 8.33 | 47.22 | 53.19 | - | 9.09 | 60 |
| GDD-116 | 23.08 | 46.67 | 15.38 | 42.31 | 13.64 | 31.82 | 53.66 | 57.14 | 50 | - | 18 | 10 |
| GDD-118 | 30.77 | 40 | 30.77 | 15.38 | 13.64 | 36.36 | 53.66 | 57.14 | 50 | - | 9 | 30 |
| GDD-120 | 30.77 | 40 | 15.38 | 19.23 | 18.18 | 40.91 | 56.10 | 59.18 | 37.50 | - | 0 | 100 |
| GDD-124 | 23.08 | 43.33 | 15.38 | 19.23 | 13.64 | 40.91 | 36.59 | 55.10 | 43.75 | - | 15 | 10 |
| GDD-126 | 30.77 | 36.67 | 23.08 | 19.23 | 13.64 | 54.55 | 56.10 | 57.14 | 0 | - | 15 | 20 |
| GDD-130 | 23.08 | 43.33 | 15.38 | 7.69 | 9.09 | 40.91 | 46.34 | 51.02 | 56.25 | - | 10 | 30 |
| GDD-132 | 30.77 | 43.33 | 23.08 | 26.92 | 18.18 | 27.27 | 58.54 | 53.06 | 56.25 | - | 14 | 10 |
| GDD-136 | 6.67 | 50 | 13 | 24 | 14.29 | 41.67 | 58.33 | 64.62 | 57.14 | - | 20 | 50 |
| Young urea goes out | 5 | 11 | 7 | 0 | 8 | 4 | 3 | 22 | 14 | 3.45 | 12.50 | 40 |
The data of fungicidal activity are the measurement result of 50 mcg/ml; ND: undetermined; *: small cabbage moth; #: mosquito larvae
Table 4 high reactivity 4-of the present invention replaces-1,2, and 3-thiadiazole formoxyl ureide compound V and high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII mixes the preparation processing method of using with commercially available agricultural chemical
Claims (10)
1. a class 2, the 3-thiadiazole formoxyl ureide compound is characterized in that: have the general structure shown in V and VII:
Wherein: R
1Be selected from following substituting group: H, CH
3, CF
3, Ph, CHF
2, CH
2X, described X are halogen atom F, Cl, Br, I, cyclopropyl, substituted-phenyl, substituted heterocycle aryl; R
2, R
3, R
4, R
5Be selected from following substituting group: H, F, Cl, Br, I, CF
3, CCl
3, OCF
3, allyl group, propargyl, aldehyde radical, hydroxyl, amido, itrile group, ester group, carboxyl, C1-C12 cycloalkyl, cycloalkenyl group, cycloalkynyl radical, various straight or branched that 1 to 10 halogen atom replaces or cyclic alkyl, thiazolinyl, alkynyl, Ph, the CHF of containing of straight or branched alkyl, thiazolinyl, alkynyl, C3-C12
2, CH
2X or-OR
6Group, described X is the group of halogen atom F, Cl, Br, I, cyclopropyl, substituted-phenyl, described R
6Be the cycloalkyl of the straight or branched that is selected from C1-C12 or cyclic alkyl, thiazolinyl, alkynyl, C3-C12, cycloalkenyl group, cycloalkynyl radical, various straight or branched that 1 to 10 halogen atom replaces or cyclic alkyl, thiazolinyl, the alkynyl of containing; Alkyl wherein, thiazolinyl, alkynyl are selected from the direct-connected or side chain of C1-C12 or cyclic alkyl, thiazolinyl, alkynyl, these alkyl, thiazolinyl, alkynyl contain 1 to 10 halogen atom, various substituted aryl or the heterocyclic aryl that contains 1 to 10 halogen atoms, halogen atom wherein is meant F, Cl, Br, I atom, can directly link with aromatic ring, also can directly be connected with alkyl, thiazolinyl, the alkynyl on the aromatic ring, described alkyl, thiazolinyl, alkynyl are selected from the direct-connected or side chain of C1-C12 or cyclic alkane, thiazolinyl, alkynyl; Described aryl is meant the phenyl of various replacements or pyridyl, thiazolyl, thiadiazolyl group, pyrimidyl, thienyl, triazolyl, tetrazole base, pyrryl, furyl, pyrazinyl, thiazinyl, the triazinyl of various replacements; R
2, R
3, R
4, R
5The phenyl that replaces also is selected from substituted benzene benzothiazolyl, substituted anthraquinone base, substituted naphthyl; Q is for being selected from benzene-1,2-two bases, benzene-1,3-two bases, benzene-1,4-two bases, pyridine-2,6-two bases, 2-oil of mirbane-1,4-two bases, naphthalene-1,8-two bases, 2-cyano group vinyl cyanide-1,1-two bases, 4-methylbenzene-1,2-two bases, 4-phenyl-1,3,5-triazine-2,6-two bases, hexamethylene-1,2-two bases, 4-oil of mirbane-1,2-two bases, 4-methylbenzene-1,3-two bases, dicyclohexyl methylene radical-4,4 '-two bases, anthraquinone-1,4-two bases, 4,4-dimethyl cyclohexane-1-base-3-methylene radical-, pyridine-2,3-two bases, pyridine-2,4-two bases, pyridine-2,5-two bases, pyridine-2,6-two bases, pyridine-3,4-two bases, pyridine-3,5-two bases, thiophene-2,3-two bases, thiophene-2,4-two bases, thiophene-2,5-two bases, thiophene-3,4-two bases, furans-2,3-two bases, furans-2,4-two bases, furans-2,5-two bases, furans-3,4-two bases, 3,4-diaminostilbene, 2, the 5-oxadiazole, 2,3-diamino-5,6-dicyano pyrazine, 2, the group of aromatic diamines base such as 3-diamino-5-bromo-pyrazine or heteroaromatic two amidos.
2. claim 1 is described 1,2, the synthetic method of 3-thiadiazole formoxyl ureide compound V and VII, and concrete synthetic route is as follows:
Wherein: substituent R
1, R
2, R
3, R
4, R
5For being selected from the group shown in claim 1;
Wherein, substituent R
1With Q be the group that is selected from shown in claim 1; Concrete steps are as follows:
A. intermediate 4-replaces-1,2, the preparation of 3-thiadiazole formoxyl chlorine I:
Intermediate 4-replaces-1,2,3-thiadiazole formoxyl chlorine I prepares as follows: 0.067 mole intermediate 4-is replaced-1,2,3-thiadiazoles 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, yield 85% under 2000Pa, intermediate 4-replaces-1,2, the sealing of 3-thiadiazole formoxyl chlorine is kept in the moisture eliminator standby, and intermediate 4-replaces-1,2, the amount of 3-thiadiazole formoxyl chlorine I preparation enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles;
B. intermediate 4-replaces-1,2, the preparation of 3-thiobizole formanide II:
In 500 milliliters two-mouth bottle, the ammoniacal liquor that adds 30 milliliter 25%, 5 milliliters triethylamine, 50 milliliters tetrahydrofuran (THF), the intermediate 4-replacement-1,2 that the Dropwise 5 gram dilute through 10 milliliters of tetrahydrofuran (THF)s under the cooling of ice bath and mechanical stirring, 3-thiadiazole formoxyl chlorine I, dropwised in 15 minutes, ice bath continues down to stir 2 hours, at room temperature stirs then 7 hours; After reaction finishes, use the separating funnel separatory, 15 milliliters of tetrahydrofuran (THF) aqueous layer extracted 3 times, merging organic layer, spend the night with anhydrous sodium sulfate drying, suction filtration is removed anhydrous sodium sulphate, and rotary evaporation removes and desolvates, and the adularescent chip solid generates, for intermediate 4-replaces-1,2,3-thiobizole formanide II; The amount of synthetic compound II enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles;
C. intermediate 4-replaces-1,2, the preparation of 3-thiadiazole formoxyl based isocyanate III:
Get 100 milliliters there-necked flask, add 2 gram intermediate 4-and replace-1,2,1 of 3-thiobizole formanide II and 15 milliliters, the 2-ethylene dichloride stirs, acid amides is uniformly dispersed in solvent, drip 4.3 grams through 5 milliliter 1 with dropping funnel under ice bath, the oxalyl chloride that the 2-ethylene dichloride diluted dropwised in 30 minutes, stirred 1 hour under the room temperature then, reheat to 80 degree centigrade backflow 7 hours, reaction solution becomes muddiness from white and changes shallow yellow transparent solution into, and heating back color deepens gradually; After reaction finished, rotary evaporation removed and desolvates to such an extent that intermediate 4-replaces-1,2, and 3-thiadiazole formoxyl based isocyanate III need not be further purified and be directly used in subsequent reactions; The amount of synthetic compound III enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles;
D. high reactivity 4-replaces-1,2, the preparation of 3-thiadiazole formoxyl ureide compound V:
In 100 milliliters of round-bottomed flasks, add aminated compounds IV that 2.7 mmole halogens replace and 20 milliliter 1, the 2-ethylene dichloride, stir and drip 3 mmole intermediate 4-replacement-1 down, 2,3-thiadiazole formoxyl based isocyanate III dropwised in 15 minutes, produced precipitation immediately, at room temperature stirred 8 hours, after reaction finishes, leave standstill suction filtration separate solid and solvent, solid is product V, the filtrate rotary evaporation removes and desolvates, and is 1: 3 ethyl acetate with volume ratio: put into refrigerator behind the sherwood oil recrystallization, separate out solid, the combining solid product, be 1: 3 ethyl acetate with volume ratio: the petroleum ether after drying gets product; With the pure product calculated yield of gained, measure fusing point and
1The mensuration of HNMR, the amount of synthetic compound V enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles;
E. the preparation of high reactivity two (4-replaces-1,2,3-thiadiazoles-5-formyl urea) compounds VII:
In 100 milliliters of round-bottomed flasks, add diamine compounds H
2N-Q-NH
2VI, drip 1 again, the 2-ethylene dichloride and be stirred to aminated compounds just fully the dissolving till, under agitation drip 3 mmole 4-methyl isophthalic acids then, 2,3-thiadiazoles-5-formyl radical isocyanic ester III, diamines in molar ratio: isocyanic ester is calculating in 0.45: 1, dropwises in 20 minutes, reflux is 1 hour then, at room temperature stir 8 hours afterreactions and finish, the standing and reacting mixture, suction filtration is collected solid and is crude product VII; Filtrate is put into refrigerator and cooled has solid to separate out after but, and combining solid and washing are dry, and be 1: 3 ethyl acetate with volume ratio: petroleum ether gets the pure product of product; With the pure product calculated yield of gained, measure fusing point and
1The mensuration of H NMR, the amount of synthetic compound VII enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles.
3. sterilant is characterized in that: claim 1 is described 1,2, and 3-thiadiazole formoxyl ureide compound V and VII and agricultural go up the purposes of acceptable assistant in the preparation sterilant.
4. sterilant is characterized in that: claim 1 is described 1,2, and 3-thiadiazole formoxyl ureide compound V and VII and agricultural go up the purposes of acceptable assistant in the preparation sterilant.
5. Antiphytoviral medicament is characterized in that: claim 1 is described 1,2, and 3-thiadiazole formoxyl ureide compound V and VII and agricultural go up the purposes of acceptable assistant in preparation Antiphytoviral medicament.
6. a kind of plant activator is characterized in that: claim 1 is described 1,2, and 3-thiadiazole formoxyl ureide compound V and VII and agricultural go up acceptable assistant is used for anti-Plant diseases of inducing plant and virus disease at preparation plant activator purposes.
7. parasiticidal composition, it is characterized in that: claim 1 described 1,2,3-thiadiazole formoxyl ureide compound V and VII 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 described 1,2,3-thiadiazole formoxyl ureide compound V and the VII total quality percentage composition in composition is 1%-90%, claim 1 described 1,2, the ratio of 3-thiadiazole formoxyl ureide compound V and VII and commercially available agricultural chemical is mass percent 1%: 99% to 99%: 1%; The formulation of processing is selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, 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, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, the capsule granula, capsule suspension, can disperse dense dose, pulvis, dry mixing kind pulvis, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the seed treatment suspension agent, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, big granula, the drift pulvis, granula, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix and adorn agent, the medicine lacquer, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, plant the clothing agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, soluble powder, the seed treatment water solube powder, the ultra-low volume suspension agent, tablet, follow the trail of pulvis, ultra low volume liquids, the steam releasing agent, water-dispersible granules, wettable powder, in the wet-mixing kind water-dispersible powder any one; Wherein said plant is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, 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, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape.
8. desinsection, antiviral agent or desinsection, the composition of inducing plant antiviral agent, it is characterized in that: claim 1 described 1,2,3-thiadiazole formoxyl ureide compound V and VII and agricultural go up acceptable assistant and be selected from diazosulfide, tiadinil, different metsulfovax, 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, allyl isothiazole, well ridge azanol, in the jingganmycin any one or two kinds of combined preparation become anti-plant virus agent or plant activator and the purposes in Antiphytoviral or inducing plant control viral diseases of plants thereof; Claim 1 described 1,2,3-thiadiazole formoxyl ureide compound V and the VII total quality percentage composition in composition is 1%-90%, claim 1 described 1,2, the ratio of 3-thiadiazole formoxyl ureide compound V and VII and above-mentioned medicament is mass percent 1%: 99% to 99%: 1%; Wherein said desinsection, the formulation of antiviral agent is selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, 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, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, the capsule granula, capsule suspension, can disperse dense dose, pulvis, dry mixing kind pulvis, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the seed treatment suspension agent, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, big granula, the drift pulvis, granula, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix and adorn agent, the medicine lacquer, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, plant the clothing agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, soluble powder, the seed treatment water solube powder, the ultra-low volume suspension agent, tablet, follow the trail of pulvis, ultra low volume liquids, the steam releasing agent, water-dispersible granules, wettable powder, in the wet-mixing kind water-dispersible powder any one; Wherein said plant is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, 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, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape.
9.；；：11；2；3-VVII；；；；4--1；2；3--5-；4--1；2；3--5-；4--1；2，3--5-；DL-β-；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；；。 Claim 1 described 1,2,3-thiadiazole formoxyl ureide compound V and the VII total quality percentage composition in composition is 1%-90%, claim 1 described 1,2, the ratio of 3-thiadiazole formoxyl ureide compound V and VII and commercially available agricultural chemical is mass percent 1%: 99% to 99%: 1%; The formulation of wherein said sterilant is selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, 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, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, the capsule granula, capsule suspension, can disperse dense dose, pulvis, dry mixing kind pulvis, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the seed treatment suspension agent, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, big granula, the drift pulvis, granula, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix and adorn agent, the medicine lacquer, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, plant the clothing agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, soluble powder, the seed treatment water solube powder, the ultra-low volume suspension agent, tablet, follow the trail of pulvis, ultra low volume liquids, the steam releasing agent, water-dispersible granules, wettable powder, in the wet-mixing kind water-dispersible powder any one; Wherein said plant is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, 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, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape.
10. claim 1 is described 1,2, and 3-thiadiazole formoxyl ureide compound V and VII and commercially available agricultural chemical are combined to form the complete processing of pesticide preparation.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0193249A2 (en) * | 1985-03-01 | 1986-09-03 | Duphar International Research B.V | Benzoyl urea derivatives having ati-tumor activity |
| WO2008074427A1 (en) * | 2006-12-21 | 2008-06-26 | Syngenta Participations Ag | Insecticidal compounds |
| CN101863856A (en) * | 2010-06-12 | 2010-10-20 | 利尔化学股份有限公司 | Bi(4-methyl-1,2,3-thiadiazole-5-phenurone) compounds and preparation method and application thereof |
| CN101899042A (en) * | 2010-06-12 | 2010-12-01 | 南开大学 | 4-substituted-1,2,3-thiadiazole formoxyl ureide compound, preparation method and application thereof |
| CN101973959A (en) * | 2010-06-12 | 2011-02-16 | 利尔化学股份有限公司 | 4-methyl-1,2,3-thiadiazole-5-formyl urea compounds and preparation method and application thereof |
-
2010
- 2010-06-12 CN CN201010198539A patent/CN101863856A/en active Pending
-
2011
- 2011-04-29 CN CN201110108876.4A patent/CN102225918B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0193249A2 (en) * | 1985-03-01 | 1986-09-03 | Duphar International Research B.V | Benzoyl urea derivatives having ati-tumor activity |
| WO2008074427A1 (en) * | 2006-12-21 | 2008-06-26 | Syngenta Participations Ag | Insecticidal compounds |
| CN101863856A (en) * | 2010-06-12 | 2010-10-20 | 利尔化学股份有限公司 | Bi(4-methyl-1,2,3-thiadiazole-5-phenurone) compounds and preparation method and application thereof |
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| CN101863856A (en) | 2010-10-20 |
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