CN101058574B - Benzo [1,2,3] thiadiazoles derivatives, synthesis method and use thereof - Google Patents
Benzo [1,2,3] thiadiazoles derivatives, synthesis method and use thereof Download PDFInfo
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Abstract
The invention discloses a benzothiadiazole formamide derivant and synthesizing method and direct anti-tobacco mosaic virus activity and tobacco mosaic virus induced activity and bacteriostatic activity, and relates to a heterocyclic compound with 1, 2-diazole condensed with carbon ring, which contains 10 substituted benzo [1,2,3] thiadiazole-7-formamide derivant. The invention can inhibit the activity of tobacco mosaic virus and induced activity of tobacco mosaic virus as well as agricultural fungi.
Description
Technical field
Technical scheme of the present invention relates to the heterogeneous ring compound that contains 1,2-diazole of condensed with carbocyclic ring, is specifically related to diazosulfide derivative.
Background technology
Plant inducing anti-disease activator mechanism of action novelty, environmentally friendly, belong to the environment friendly agricultural category, now researched and developed successful principal item S-methyl benzo [1 has been arranged, 2,3] (english abbreviation is BTH to thiadiazoles-7-carbothioic acid ester, english common name: acibenzolar-S-methyl), 2,6-dichloro-isonicotinic acid and beta-aminobutyric acid, methyl jasmonate, allyl isothiazole and tiadinil (Bao Lili such as (english common name: Tiadinil are called for short TDL), Liu Fengli, Fan Zhijin has active lead compound of plant inducing anti-disease and structural modification thereof, the Pesticide Science journal, 2005,7 (3): 201-209; Michiko Yasuda; HideoNakashita; Shigeo Yoshida; Tiadinil, a novel class of activator of systemic acquired resistance, induces defense gene expression and disease resistance in tobacco.Japanese Pesticide Science, 2004,29:46-49).The contriver had once set up the screening system of plant inducing anti-disease activator inducing anti-disease activity, about the report situation of the research of diazosulfide inducing anti-disease activity and patent documentation has been summarised in the contriver recently in the background technology of the patent document of application, simultaneously, the contriver has synthesized the derivative of some BTH, part of compounds demonstrates the evoking tobacco resisting tobacco mosaic virus activity (Fan Zhijin etc. of (being called for short TMV), the screening of diazosulfide derivative and synthetic method thereof and inducing anti-disease activity, People's Republic of China's national inventing patent, application number: 200510013111.7, publication number: CN1680342A; Fan Zhijin etc., the activity of diazosulfide derivative and synthetic method thereof and evoking tobacco resisting tobacco mosaic virus, People's Republic of China's national inventing patent, application number: 200510014378.8), the general structure of this compounds can represent as:
At home and abroad in the disclosed diazosulfide derivative of patent documentation, except the patent of applicant oneself application, all do not relate to its evoking tobacco resisting tobacco mosaic virus activity of (being called for short TMV), do not carry out the research of relevant inducing anti-disease bioactivity screening yet, in order further to seek novel B TH derivative with higher induced activity, for structure activity relationship (QSAR) research lays the foundation, patent of the present invention is carried out structural modification in a basic enterprising step of early-stage Study, has synthesized 10 new compounds of not seeing bibliographical information.
Summary of the invention
Technical problem to be solved by this invention is: diazosulfide derivative and the synthetic method and the active screening of the anti-TMV of evoking tobacco of evoking tobacco resisting tobacco mosaic virus are provided, and its screening system comprises the screening of induced activity of stripped screening and live body and the screening of active mensuration of phenylalanine ammonia lyase (PAL) and bacteriostatic activity.
The present invention solves this technical problem the technical scheme that is adopted: the chemical structure of general formula of the diazosulfide derivative of evoking tobacco resisting tobacco mosaic virus is:
Wherein: R
1And R
2Be respectively hydrogen, pyridine-2-base, 1,3-thiazoles-2-base, 4,6-dimethyl pyrimidine-2-base, n-propyl, sec.-propyl, normal-butyl, 1-cyano group-1,2-dimethyl propyl, 1-cyano group-1,2,2-trimethylammonium propyl group, benzoyl, R
1And R
2And the common six-ring piperidine ring that contains 5 carbon atoms and 1 nitrogen-atoms of forming of the nitrogen-atoms that links with carbonyl, position or contraposition have the substituting group of ethoxycarbonyl between nitrogen heteroatom.
Its concrete chemical structural formula is expressed as follows:
I. benzo [1,2,3] thiadiazoles-7-carboxamides derivatives class:
The synthetic method of the diazosulfide derivative of evoking tobacco resisting tobacco mosaic virus of the present invention is as follows:
Specifically be divided into following steps:
A. the preparation of benzo [1,2,3] thiadiazoles-7-formyl chloride:
The benzo [1 that in the there-necked flask of 500mL, adds aequum, 2,3] thiadiazoles-7-formic acid, and the toluene of the no water treatment of process, DMF and thionyl chloride, every gram benzo [1,2,3] thiadiazoles-7-formic acid adds the toluene of 7.4mL through no water treatment approximately, 0.037mL DMF and the thionyl chloride of 0.7mL, slow intensification degree to 80～90 ℃, keep this temperature to continue reaction 6 hours, cooled and filtered, the filtrate decompression steaming removes unnecessary thionyl chloride and precipitation and gets product benzo [1,2,3] thiadiazoles-7-formyl chloride, product need not purifying and are kept at and get single step reaction in the moisture eliminator ready and directly use;
B. the preparation of the benzo of evoking tobacco resisting tobacco mosaic virus [1,2,3] thiadiazoles derivative:
Benzo [1,2,3] preparation of thiadiazoles-7-carboxamides derivatives: in the there-necked flask of 100mL, add 5mmol amine, absolute anhydrous tetrahydro furan 25mL and 6mmol sodium hydride, the sodium salt suspension for preparing corresponding amine, refluxed 3 hours and cooling mixture, Dropwise 5 mmol benzo [1 under ice bath, 2,3] the absolute anhydrous tetrahydrofuran solution of 15mL of thiadiazoles-7-formyl chloride, cooling was stirred 2 hours down, heated up gradually and reflux 6 hours, cooled and filtered, filtrate is concentrating under reduced pressure on Rotary Evaporators, get pure product with purification by silica gel column chromatography, used eluent is 60～90 ℃ sherwood oil and an ethyl acetate, and their volume ratio is 3: 1, and the consumption of above-claimed cpd can or dwindle by corresponding proportion expansion;
The screening method of diazosulfide derivative evoking tobacco activity of resisting tobacco mosaic virus of the present invention is as follows:
I. the selection of standard plant inducing anti-disease activator: selecting diazosulfide (BTH) and tiadinil (TDL) is the plant inducing anti-disease activator of standard, and vitro Screening adopts 500 μ g/mL; The Evaluation on effect of inducing live body adopts the concentration of 100 μ g/mL or 0.1mol/L;
II. the screening method of direct antiviral activity exsomatizes: test compound is mixed with the 500 μ g/mL solution that contain micro-tensio-active agent soil temperature 80, with phosphoric acid buffer TMV virus crude extract is diluted to suitable concentration, behind the frictional inoculation TMV, with blade along in arteries and veins to cuing open, about half leaf immerse respectively in test compound solution and the clear water, representative is handled and blank respectively, take out after 30 minutes, put the cultivation of preserving moisture under 23 ± 1 ℃ the illumination, observe them after 3 days and produce the quantity of withered spot, the record incidence, be calculated as follows out the directly relative effect of the anti-TMV of test compound, 3 repetitions are established in each processing, standard chemicals treatment contrast again except that blank; The relative effect of test compounds is divided into 4 grades: A, B, C, D, and concrete data are the A level: relative effect＞50%, for excellent; The B level: relative effect 30～50%, for very; The C level: relative effect 20～30%, in; The D level: relative effect＜20%, for poor,
Wherein, X is direct inhibiting rate or the relative effect of compound to TMV, unit: %
CK is the average withered spot number that clear water contrasts half leaf, unit: individual
A is the average withered spot number of chemicals treatment half leaf, unit: individual;
III. the screening method of live body inducing anti-disease cytotoxic activity: with the common cigarette of seedling age unanimity, 3 basins are one group, cigarette seedling respectively at inoculation pre-treatment in preceding 7 days, processing mode comprises: spray test compound solution 2 to 3 times, each 20mL, the 7th day frictional inoculation TMV on the tobacco leaf that newly grows, place its growth optimal temperature and the following cultivation of illumination after 3 days the cigarette seedling, check incidence, comprehensive scab number is calculated as follows out the inducing anti-disease toxic effect fruit of test compound to TMV, 3 repetitions are established in each processing, and contrast divides blank and standard chemicals treatment to contrast 2 kinds; The relative effect of test compounds is divided into 4 grades: A, B, C, D, and concrete data are the A level: induce effect＞70%, for excellent; B level: induce effect 70～50%, for very; C level: induce effect 30～50%, for poor; The D level: induce effect＜30% to be considered as not having and induce effect,
Wherein, R is the induce effect of new compound to the anti-TMV of tobacco, unit: %
CK is the average withered spot number of clear water contrast blade, unit: individual
I is for inducing the average withered spot number of handling rear blade, unit: individual through compound;
IV. the screening method of fungicidal activity: adopt thalli growth rate assay method (Mycelium growth rate test), detailed process is, get the 5mg 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 μ g/mL, reagent agent is respectively drawn 1mL under aseptic condition inject in the culture dish, add the 9mL substratum more respectively, make 50 μ g/mL pastille flat boards after shaking up, do blank with the flat board that adds the 1mL aqua sterilisa, punch tool with diameter 4mm cuts the bacterium dish along the mycelia outer rim, move on the pastille flat board, be equilateral triangle and put, every processing repeats 3 times, culture dish is placed on cultivation in 24 ± 1 ℃ of constant incubators, " Invest, Then Investigate " was respectively handled bacterium dish expansion diameter in 48 hours, averaged, and relatively calculated relative bacteriostasis rate with blank.Comprise gibberella saubinetii (Gibberellazeae), tomato early epidemic disease (Alternaria), asparagus stem withered (Phoma asparagi solani), apple wheel line (Physalosporapiricola) and peanut foxiness (Cercospora arachidicola) for the examination pathogenic fungi.
The invention has the beneficial effects as follows: diazosulfide is a kind of plant inducing anti-disease activator of standard, utilize the last patent of invention of applicant to set up the screening system, successfully inducing tobacco plant TMV to be produced on the basis of good antiviral activity, the further successful application of the present invention this system carry out the screening of inducing anti-disease activity, step of going forward side by side is carried out the screening of bacteriostatic activity, and The selection result finds that part of compounds has the activity of evoking tobacco resisting tobacco mosaic virus preferably and suppresses the activity of pathogenic fungi growth.
The present invention will more specifically describe the synthetic and biological activity of diazosulfide analog derivative by specific preparation and biological activity determination embodiment, but described embodiment only is used for specific description the present invention and unrestricted the present invention, and concrete embodiment is as follows:
Embodiment 1
The preparation of benzo [1,2,3] thiadiazoles-7-formyl chloride:
Add 27.0g benzo [1,2,3] thiadiazoles-7-formic acid in the there-necked flask of 500mL, 200mL is through the toluene of no water treatment, the DMF of 1mL, the SOCl of 20mL
2, slowly degree of intensification is to 80～90 ℃, keeps this temperature to continue reaction 6 hours, cooled and filtered, and the filtrate decompression precipitation gets product benzo [1,2,3] thiadiazoles-7-formyl chloride 28g, and product need not purifying and is kept at and gets single step reaction in the moisture eliminator ready and directly use.
Embodiment 2
Synthetic and the structure of compd B 2 is identified:
In the there-necked flask of 100mL, add 0.47g 2-aminopyridine, absolute anhydrous tetrahydro furan 25mL and 0.32g sodium hydride, the sodium salt suspension for preparing corresponding amine, stirring at normal temperature 1.5 hours, drip 1g benzo [1,2,3] the absolute anhydrous tetrahydrofuran solution of 15mL of thiadiazoles-7-formyl chloride, stirring at normal temperature 2 hours, reacted after-filtration, the decompression precipitation gets crude product 0.52g, and yield 41.1% gets pure product with purification by silica gel column chromatography, used eluent is 60～90 ℃ sherwood oil and an ethyl acetate, and their volume ratio is 2: 1.Measure fusing point and
1H NMR, its chemical structural formula and physical and chemical parameter see Table 1 and table 2, by table 1 and table 2 as seen, and this compound
1H NMR shows and the corresponding chemical shift of its structure that the number of H and its structure are coincide, and MS measures the m/z peak that corresponding M+1 occurs, and corresponding skeleton absorption peak appears in IR, and the maximum absorption band of UV scanning appears at 380.0nm and 280.0nm place.
Embodiment 3
Synthetic and the structure of compd B 4 is identified:
In the there-necked flask of 100mL, add 0.50g thiazolamine, absolute anhydrous tetrahydro furan 25mL and 0.23g sodium hydride, the sodium salt suspension for preparing corresponding amine, stirring at normal temperature 1.5 hours, drip 1g benzo [1,2,3] the absolute anhydrous tetrahydrofuran solution of 15mL of thiadiazoles-7-formyl chloride, stirring at normal temperature 2 hours, reacted after-filtration, the decompression precipitation gets crude product 0.71g, and yield 54.2% gets pure product with purification by silica gel column chromatography, used eluent is 60～90 ℃ sherwood oil and an ethyl acetate, and their volume ratio is 5: 1.Measure fusing point and
1H NMR, its chemical structural formula and physical and chemical parameter see Table 1 and table 2, by table 1 and table 2 as seen, and this compound
1H NMR shows and the corresponding chemical shift of its structure that the number of H and its structure are coincide, and MS measures the m/z peak that corresponding M-1 occurs, and corresponding skeleton absorption peak appears in IR, and the maximum absorption band of UV scanning appears at 327.0nm and 264.0nm place.
Embodiment 4
Synthetic and the structure of B8 is identified:
In the there-necked flask of 100mL, add 0.62g 4,6-dimethyl pyrimidine-2-amine, absolute anhydrous tetrahydro furan 25mL and 0.23g sodium hydride, the sodium salt suspension for preparing corresponding amine, stirring at normal temperature 1.5 hours, drip 1g benzo [1,2,3] the absolute anhydrous tetrahydrofuran solution of 15mL of thiadiazoles-7-formyl chloride, stirring at normal temperature 2 hours has been reacted after-filtration, and the decompression precipitation gets crude product 0.82g, yield 58.6%, get pure product with purification by silica gel column chromatography, used eluent is 60～90 ℃ sherwood oil and an ethyl acetate, and their volume ratio is 3: 1.Measure fusing point and
1H NMR, its chemical structural formula and physical and chemical parameter see Table 1 and table 2, by table 1 and table 2 as seen, and this compound
1H NMR shows and the corresponding chemical shift of its structure that the number of H and its structure are coincide, and MS measures the m/z peak that corresponding M+1 occurs, and corresponding skeleton absorption peak appears in IR, and the maximum absorption band of UV scanning appears at 296.0nm and 268.0nm place.
Synthetic and the structure of B9 is identified:
In the there-necked flask of 100mL, add 0.79g piperidines-3-carboxylic acid, ethyl ester, absolute anhydrous tetrahydro furan 25mL and 0.23g sodium hydride, the sodium salt suspension for preparing corresponding amine, stirring at normal temperature 1.5 hours, drip 1g benzo [1,2,3] the absolute anhydrous tetrahydrofuran solution of 15mL of thiadiazoles-7-formyl chloride, stirring at normal temperature 2 hours, reacted after-filtration, the decompression precipitation gets crude product 0.71g, and yield 44.5% gets pure product with purification by silica gel column chromatography, used eluent is 60～90 ℃ sherwood oil and an ethyl acetate, and their volume ratio is 2: 1.Measure fusing point and
1HNMR, its chemical structural formula and physical and chemical parameter see Table 1 and table 2, by table 1 and table 2 as seen, and this compound
1H NMR shows and the corresponding chemical shift of its structure that the number of H and its structure are coincide, and MS measures the m/z peak that corresponding M+1 occurs, and corresponding skeleton absorption peak appears in IR, and the maximum absorption band of UV scanning appears at 315.0nm and 236.0nm place.
Embodiment 6
Synthetic and the structure of B10 is identified:
In the there-necked flask of 100mL, add 0.79g piperidines-4-carboxylic acid, ethyl ester, absolute anhydrous tetrahydro furan 25mL and 0.23g sodium hydride, the sodium salt suspension for preparing corresponding amine, stirring at normal temperature 1.5 hours, drip 1g benzo [1,2,3] the absolute anhydrous tetrahydrofuran solution of 15mL of thiadiazoles-7-formyl chloride, stirring at normal temperature 2 hours, reacted after-filtration, the decompression precipitation gets crude product 1.00g, and yield 62.6% gets pure product with purification by silica gel column chromatography, used eluent is 60～90 ℃ sherwood oil and an ethyl acetate, and their volume ratio is 4: 1.Measure fusing point and
1HNMR, its chemical structural formula and physical and chemical parameter see Table 1 and table 2, by table 1 and table 2 as seen, and this compound
1H NMR shows and the corresponding chemical shift of its structure that the number of H and its structure are coincide, and MS measures the m/z peak that corresponding M+Na occurs, and corresponding skeleton absorption peak appears in IR, and the maximum absorption band of UV scanning appears at 316.0nm and 236.0nm place.
Embodiment 7
Synthetic and the structure of B11 is identified:
In the there-necked flask of 100mL, add 0.74g 2-amino-2,3-dimethylbutane nitrile, 20ml1, the 2-ethylene dichloride, the 1.64ml triethylamine drips 1g benzo [1 under the stirring at normal temperature, 2,3] 10mL1 of thiadiazoles-7-formyl chloride, 2-dichloroethane solution, stirring at normal temperature 2 hours, react back solution and used hydrochloric acid respectively, saturated sodium bicarbonate aqueous solution, washing, anhydrous sodium sulfate drying, filter, the decompression precipitation gets crude product 0.87g, and yield 63.5% gets pure product with purification by silica gel column chromatography, used eluent is 60～90 ℃ sherwood oil and an ethyl acetate, and their volume ratio is 4: 1.Measure fusing point and
1H NMR, its chemical structural formula and physical and chemical parameter see Table 1 and table 2, by table 1 and table 2 as seen, and this compound
1H NMR shows and the corresponding chemical shift of its structure that the number of H and its structure are coincide, and MS measures the m/z peak that corresponding M-1 occurs, and corresponding skeleton absorption peak appears in IR, and the maximum absorption band of UV scanning appears at 316.0nm and 236.0nm place.
Embodiment 8
Synthetic and the structure of B14 is identified:
In the there-necked flask of 100mL, add 0.83g 2-amino-2,3,3-triptane nitrile, 20ml1, the 2-ethylene dichloride, 1.64ml triethylamine, drip the 10mL1 of 1g benzo [1,2,3] thiadiazoles-7-formyl chloride under the stirring at normal temperature, the 2-dichloroethane solution, stirring at normal temperature 2 hours has been reacted back solution and has been used hydrochloric acid, saturated sodium bicarbonate aqueous solution respectively, washing, anhydrous sodium sulfate drying filters, and the decompression precipitation gets crude product 0.56g, yield 38.9%, get pure product with purification by silica gel column chromatography, used eluent is 60～90 ℃ sherwood oil and an ethyl acetate, and their volume ratio is 3: 1.Measure fusing point and
1H NMR, its chemical structural formula and physical and chemical parameter see Table 1 and table 2, by table 1 and table 2 as seen, and this compound
1H NMR shows and the corresponding chemical shift of its structure that the number of H and its structure are coincide, and MS measures the m/z peak that corresponding M+1 occurs, and corresponding skeleton absorption peak appears in IR, and the maximum absorption band of UV scanning appears at 315.0nm and 236.0nm place.
Embodiment 9
Synthetic and the structure of BW5 is identified:
In the there-necked flask of 100mL, add 0.82g benzoyl Isopropylamine, absolute anhydrous tetrahydro furan 20mL and 0.23g sodium hydride, the sodium salt suspension for preparing corresponding amine, stirring at normal temperature refluxed 4 hours after 1 hour, drip 1g benzo [1 after being cooled to normal temperature, 2,3] the absolute anhydrous tetrahydrofuran solution of 10mL of thiadiazoles-7-formyl chloride, stirring at normal temperature refluxed 2 hours after 1 hour, cooled and filtered, the decompression precipitation gets crude product 0.7g, and yield 44.1% gets pure product with purification by silica gel column chromatography, used eluent is 60～90 ℃ sherwood oil and an ethyl acetate, and their volume ratio is 16: 1.Measure fusing point and
1H NMR, its chemical structural formula and physical and chemical parameter see Table 1 and table 2, by table 1 and table 2 as seen, and this compound
1H NMR shows and the corresponding chemical shift of its structure that the number of H and its structure are coincide, and MS measures the m/z peak that corresponding M-1 occurs, and corresponding skeleton absorption peak appears in IR, and the maximum absorption band of UV scanning appears at the 380.0nm place.
Embodiment 10
Synthetic and the structure of BW8 is identified:
In the there-necked flask of 100mL, add 0.64g benzoyl n-Butyl Amine 99, absolute anhydrous tetrahydro furan 20mL and 0.23g sodium hydride, the sodium salt suspension for preparing corresponding amine, stirring at normal temperature refluxed 4 hours after 1 hour, drip 0.72g benzo [1 after being cooled to normal temperature, 2,3] the absolute anhydrous tetrahydrofuran solution of 10mL of thiadiazoles-7-formyl chloride, stirring at normal temperature refluxed 2 hours after 1 hour, cooled and filtered, the decompression precipitation gets crude product 0.68g, and yield 56.1% gets pure product with purification by silica gel column chromatography, used eluent is 60～90 ℃ sherwood oil and an ethyl acetate, and their volume ratio is 15: 1.Measure fusing point and
1H NMR, its chemical structural formula and physical and chemical parameter see Table 1 and table 2, by table 1 and table 2 as seen, and this compound
1H NMR shows and the corresponding chemical shift of its structure that the number of H and its structure are coincide, and MS measures the m/z peak that corresponding M-1 occurs, and corresponding skeleton absorption peak appears in IR, and the maximum absorption band of UV scanning appears at 380.0nm and 260.0nm place.
Embodiment 11
Synthetic and the structure of BW16 is identified:
In the there-necked flask of 100mL, add 0.83g benzoyl Tri N-Propyl Amine, absolute anhydrous tetrahydro furan 20mL and 0.21g sodium hydride, the sodium salt suspension for preparing corresponding amine, stirring at normal temperature refluxed 4 hours after 1 hour, drip 0.83g benzo [1 after being cooled to normal temperature, 2,3] the absolute anhydrous tetrahydrofuran solution of 10mL of thiadiazoles-7-formyl chloride, stirring at normal temperature refluxed 2 hours after 1 hour, cooled and filtered, the decompression precipitation gets crude product 0.72g, and yield 52.9% gets pure product with purification by silica gel column chromatography, used eluent is 60～90 ℃ sherwood oil and an ethyl acetate, and their volume ratio is 15: 1.Measure fusing point and
1H NMR, its chemical structural formula and physical and chemical parameter see Table 1 and table 2, by table 1 and table 2 as seen, and this compound
1H NMR shows and the corresponding chemical shift of its structure that the number of H and its structure are coincide, and MS measures the m/z peak that corresponding M-1 occurs, and corresponding skeleton absorption peak appears in IR, and the maximum absorption band of UV scanning appears at 324.0nm and 234.0nm place.
Embodiment 12
The effect of benzo of the present invention [1,2,3] thiadiazoles derivative evoking tobacco resisting tobacco mosaic virus:
The biological tobacco determination test the results are shown in Table 3, table 3 shows, the plant inducing anti-disease activator BTH of standard and tiadinil and most of benzo [1 of the present invention, 2,3] all to TMV unrestraint effect, but BTH and tiadinil can produce the good resistance of TMV by evoking tobacco thiadiazoles derivative under isolated condition; Preliminary bioassay results shows, benzo [1 of the present invention, 2,3] thiadiazoles derivative BW5 has 58% antiviral activity when 500 μ g/mL, the activity that has 86% the anti-TMV of evoking tobacco during 100 μ g/mL, all compounds still have good induced activity under 0.1mmol/L concentration, greater than 55%, wherein the induced activity of B4 and BTH are suitable substantially.
Embodiment 13
The extraction and the determination of activity of phenylalanine ammonia lyase (PAL) in the tobacco plant body behind the anti-TMV of evoking tobacco of benzo of the present invention [1,2,3] thiadiazoles derivative:
The tobacco leaf that newly grow and that inoculate MV of learning from else's experience after above-claimed cpd is induced is to be measured, add 3mL 0.2mol/L borate buffer solution (pH8.8, the mercaptoethanol that contains 0.005mol/L, the EDTA of 0.001mol/L) and the polyvinylpyrrolidone (PVP) of about example weight 1/10, homogenate in ice bath.10000 rev/mins, 4 ℃ were descended centrifugal 20 minutes, and supernatant liquor is made enzyme activity determination.The mensuration system is by the borate buffer solution of 2mL 0.2mol/L pH8.8.1mL0.02mol/L L-phenylalanine and 0.8mL enzyme liquid are formed.Measure OD
290After, in 37 ℃ of water-baths 1 hour, measure OD again
290Value contrasts the enzyme-added liquid 0.8mL into borate buffer solution 3mL.The mensuration of protein content adopts Cowes light blue G250 method, is standard protein with BSA.PAL measures the results are shown in Figure of description 1, by accompanying drawing 1 as seen, compd B W7, B4 and B7 induce the interior PAL enzymic activity of back tobacco body that raising is arranged, the degree that improves is not as BTH inductive result, but more effective than inducing of another standard medicament TDL, the degree that B4 improves is the highest, can think that tentatively B4 has induced activity preferably, and B14 does not only not improve, and descends to some extent on the contrary, remains further research with the reason of this difference of the result of biological assay.
Embodiment 14
The bacteriostatic activity of benzo of the present invention [1,2,3] thiadiazoles derivative:
Thalli growth rate method measurement result sees Table 4, and table 4 shows that synthetic majority of compounds of the present invention does not all have bacteriostatic activity, and compd B 4 has good bacteriostatic activity, and it suppresses effect is 100%, further furthers investigate.
The physical and chemical parameter of table 1 The compounds of this invention
Table 2 The compounds of this invention
1H NMR and MS and IR data
The activity of the compound evoking tobacco resisting tobacco mosaic virus among table 3 the present invention
Annotate: data are average results of 3 experiments in the table
The bacteriostatic activity of the compound among table 4 the present invention
Description of drawings:
Fig. 1, the variation of PAL enzymic activity in the tobacco body after synthetic compound of the present invention is induced (average results of 3 experiments).
Claims (4)
1. a diazosulfide derivative is characterized in that it is the compound of structural formula (I), and its compound number is B4:
2. the synthetic method of the described diazosulfide derivative B4 of claim 1 is characterized in that synthetic method is:
In 100 milliliters there-necked flask, add 0.50 gram thiazolamine, 25 milliliters of absolute anhydrous tetrahydro furans and 0.23 gram sodium hydride, the sodium salt suspension for preparing corresponding amine, stirring at normal temperature 1.5 hours, drip 1 gram benzo [1,2,3] 15 milliliters of absolute anhydrous tetrahydrofuran solutions of thiadiazoles-7-formyl chloride, stirring at normal temperature 2 hours, reacted after-filtration, the decompression precipitation gets crude product 0.71 gram, and yield 54.2% gets pure product with purification by silica gel column chromatography, used eluent is the sherwood oil and the ethyl acetate of 60～90 degree, and their volume ratio is 5: 1; The consumption of compound (I) enlarges by corresponding proportion or dwindles.
3. the purposes of the described diazosulfide derivative of claim 1 in preparation evoking tobacco resisting tobacco mosaic virus medicament.
4. the purposes of the described diazosulfide derivative of claim 1 in preparation fungicidal medicament.
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|---|---|---|---|---|
| US5066661A (en) * | 1989-03-08 | 1991-11-19 | Ciba-Geigy Corporation | Agents for protecting plants against diseases |
| CN1033354C (en) * | 1987-08-21 | 1996-11-27 | 希巴-盖吉股份公司 | Compositions of 7-substituted-benzo-1,2,3-thiadiazole derivetes |
| CN1680342A (en) * | 2005-01-19 | 2005-10-12 | 南开大学 | Diazosulfide derivative and its synthesis and screening method for inducing anti-disease activity |
-
2005
- 2005-12-14 CN CN200710090312A patent/CN101058574B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033354C (en) * | 1987-08-21 | 1996-11-27 | 希巴-盖吉股份公司 | Compositions of 7-substituted-benzo-1,2,3-thiadiazole derivetes |
| US5066661A (en) * | 1989-03-08 | 1991-11-19 | Ciba-Geigy Corporation | Agents for protecting plants against diseases |
| CN1680342A (en) * | 2005-01-19 | 2005-10-12 | 南开大学 | Diazosulfide derivative and its synthesis and screening method for inducing anti-disease activity |
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