CN102731434A - Preparation and plant activate antipathogen activity of benzo carboxylate derivatives of 1,2,3-thiadiazole - Google Patents
Preparation and plant activate antipathogen activity of benzo carboxylate derivatives of 1,2,3-thiadiazole Download PDFInfo
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- CN102731434A CN102731434A CN2012102359471A CN201210235947A CN102731434A CN 102731434 A CN102731434 A CN 102731434A CN 2012102359471 A CN2012102359471 A CN 2012102359471A CN 201210235947 A CN201210235947 A CN 201210235947A CN 102731434 A CN102731434 A CN 102731434A
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Abstract
The invention provides water-oil soluble benzo[1,2,3]-thiadiazole-7-carboxylate derivatives with plant activate antipathogen activity and salts thereof. The derivatives are shown as a general formula (I, II), wherein X is an oxygen, a nitrogen atom or a sulfur atom; n is 0, 1, 2, 3, 4, 5 and so on or (CH2)n represents alkyl carrying a branched chain; Y is Cl<->, Br<->, F<->, I<->, AcO<->, acetylsalicylic acid radical, nitric acid radical, salicylic acid radical, p-toluenesulfonic acid radical, bisulfate radical or other negative ions; R<1> is alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, alkenyl of 1-6 carbon atoms, or aryl; R<2> is alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, alkenyl of 1-6 atoms, or aryl; or the R<1> and the R<2> are selected from the structure in the specification.
Description
Technical field
The present invention relates to 1,2, the preparation of the benzo ramification of carboxylic esters of 3-thiadiazoles and plant are activated anti-disease activity.
Background technology
1,2, the 3-thiadiazoles heterocyclic compounds has wide biological activity (Bakulev V A; Dehaen W.The Chemistry of 1,2,3-thiadiazole; 2004, John Wiley & Sons.Inc.), have three compounds to comprise that BTH and tiadinil (TDL) and TDZ are exactly 1 in the Pesticidal products of having succeeded in developing; 2, the verivate of 3-thiadiazoles, BTH and TDL are typical plant activator; Wherein BTH is first synthetic plant activator of succeeding in developing, and it is the product of Syngenta Co.,Ltd, is the most successful, the best compound of induced activity of exploitation at present.Benzo [1,2,3] thiadiazoles-7-carboxylate methyl ester (BTH) and verivate thereof had report in some documents; The Walter Kunz of vapour Ba-Jia Ji company etc. have also obtained this compound when the research and development sulfonylurea herbicide; But they find that first this compound can excite plant to produce SAR. subsequently, and Walter Kunz etc. carry out the synthetic and bioassay of a large amount of chemically modifieds to this compound, and have illustrated the structure activity relationship of this compounds as plant disease resistance inductor; And then comprehensive each side factor has been selected S-methyl benzo [1; 2,3] thiadiazoles-first-selected disease control compound of 7-thiocarboxylic acid (CGA245704) conduct, and commercialization has been used for agricultural.
Acibenzolar (BTH) is a kind of plant disease-resistant acvator.Itself does not have fungicidal activity and result of treatment, but it is absorbed the resistance mechanism that has activated later plant by plant, has activated the defence resistance reaction of plant self.Thereby make plant produce the self-protection effect of wide spectrum, and produce persistent resistance multiple fungi, bacterium, nematode and virus.But they have significant disadvantages as this compounds: promptly the water-soluble of them all is not very desirable, makes that its speed of action is slower, need make various preparations; Thiadiazoles-the 7-carboxylic acid is water insoluble like benzo [1,2,3]; Be slightly soluble in organic solvent, need make emulsion to it, suspension agent.
The tradition pesticide formulation are main with missible oil, wettable powder, pulvis and granule; Be accompanied by the development and the exploitation of pesticides new formulation; Following can the development towards directions such as aqua, aqueous emulsion and microemulsions; From this development trend; This just has higher requirement to the novel pesticide molecule that is about to succeed in developing, not only want efficient, low toxicity, safety and and environmental friendliness, it is certain water-soluble to hope also that simultaneously drug molecule has; If drug molecule has good water-solubility and just can be made into aqua and directly use, so not only can reduce production costs but also can reduce when drug molecule is made into certain preparation to add the environmental pollution that high amounts of solvents, tensio-active agent, auxiliary agent and permeate agent etc. are brought.From this respect, the drug molecule good water-solubility has very important significance.Simultaneously, have certain water-soluble and fat-soluble drug molecule, it is necessary also to be that medicine effectively passes microbial film.
No matter medicine is that epidermis absorbs or other approach absorb, and all need pass barrier membranes with the form of molecule.Medicine needs at first dissolving, and if medicine have ideal biopharmacy characteristic, it is diffused into the zone of lower concentration from the zone of high density, stride across cytolemma and enter into the recycle system.All microbial films contain lipid as major ingredient.Active molecule all has and contains phosphatic high polar end structure in the biofilm structure, and, in most of the cases, two highly hydrophobic hydrocarbon chains.Microbial film has bilayer structure, and the hydrophilic chain end structure is towards the water zone of both sides.Very hydrophilic medicine can't pass biomembranous lipid layer and very hydrophobic medicine because the similar reason that mixes stops wherein as a biomembranous part, thereby can not effectively get into inner tenuigenin.
The objective of the invention is to make them can reach a good balance, reduce the outer loss of organism, thereby improve the utilization ratio of medicine through improving the water-soluble and fat-soluble of phenylpropyl alcohol thiadiazole verivate.The novel cpd of these phenylpropyl alcohol thiadiazole verivates has two identical constructional features: they have part (oil soluble part) and the one-level that protonated form exists under physiology PH condition of a close ester property; Secondary, or tertiary amine group (water-soluble portion).Water-soluble-molten balance of oil like this is that medicine effectively passes microbial film institute necessary [Susan Milosovich, et al.J.Pharm.Sci., 82,227 (1993)].The amino that has positive charge has increased the solubleness of medicine greatly.This point can be seen from experimental implementation: in the product aftertreatment, the compound that does not become positive ion is dissolved in methylene dichloride and is water insoluble, add the hydrogen ion salify after, compound is dissolved in water layer, also is dissolved in methylene dichloride.As a rule, the solubleness of medicine is the step of the slowest and maximum speed limit in the absorption process.When these novel cpds are made medicament, in its molecule amino can with the phosphoric acid salt end group bonding of cytolemma.Therefore, thus very high these medicines that help of the partial concn of medicine in the microbial film outside through the zone of area with high mercury to lower concentration.After these drug molecules entered into microbial film, hydrophilic parts can promote the tenuigenin that medicine enters into the concentrated aqueous solution of semi liquid state.
Summary of the invention
The compound method that the purpose of this invention is to provide benzo [1,2,3]-thiadiazoles-7-ramification of carboxylic esters and salt thereof, this compounds have excellent plant inducing anti-disease activity.
Shown in (I and II series), table 1 and table 2 represented to see in the chemical structural formula that part is concrete to the chemical structure of general formula of benzo [1,2,3]-thiadiazoles-7-ramification of carboxylic esters and salt thereof as follows:
Wherein:
X represention oxygen atom, nitrogen-atoms, sulphur atom; N=0,1,2,3,4,5 ... Or (CH
2)
nRepresentative has the alkyl of side chain; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, or other negative ions.R
1Represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl or the aryl of a 1-6 carbon atom; R
2Represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl or the aryl of a 1-6 carbon atom; Or R
1, R
2Be selected from following structure:
The comparatively preferred compound of the present invention is:
N=1～4; X represents N, O, S; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, or other negative ions; R
1, R
2Be selected from H, C
1-C
4Alkyl or R
1=R
2Be selected from following structure:
General formula compound of the present invention (I, II) following method preparation:
Reaction path is following:
Diazosulfide formic acid and SOCl
2, PCl
3Or oxalyl chloride is dissolved in The suitable solvent, dioxane for example, benzene, toluene, ETHYLE ACETATE; THF, normal hexane, tetracol phenixin, chloroform or methylene dichloride; With organic bases such as pyridine, triethylamine is a catalyzer with DMF, temperature be 0 ℃ to boiling point down reaction made corresponding acyl chlorides in 1-24 hour.
The acyl chlorides that last step makes and (n+1)-(dialkyl group) amino-1-(mercaptan, amine) alcohol (preparing), in The suitable solvent, temperature is 0 ℃ and reacts down to boiling point and to make product (I) in 1-24 hour.Solvent can be dioxane, benzene, toluene, ETHYLE ACETATE, THF, acetone, normal hexane, tetracol phenixin, chloroform or methylene dichloride etc.Add alkaline matter, like pyridine, triethylamine, sodium hydroxide, Pottasium Hydroxide, yellow soda ash, sodium hydrogencarbonate, salt of wormwood or saleratus etc. are to reacting favourable.
Product (I) and diluted acid YH can be dissolved in product (I) in the The suitable solvent, add diluted acid YH, and temperature is 0 ℃ and reacts down to boiling point and to make product (II) in 1-24 hour.Solvent can be dioxane, benzene, toluene, ETHYLE ACETATE, THF, acetone, normal hexane, tetracol phenixin, chloroform or methylene dichloride etc.
The present invention can also explain with the compound of listing in table 1, the table 2, but not limit the present invention.
Table 1: the The compounds of this invention of part shown in general formula I
Table 2: the The compounds of this invention of part shown in general formula I I
(I, II) compound has plant activation anti-disease activity, the infringement of the fine prevention phytopathogen of ability to general formula of the present invention.Compare with existing similar compound, this compounds shows better water-solubility and anti-disease activity.
The present invention comprises that also (I, II) compound is the fungicide compsn of active ingredient with general formula.The weight percentage of active ingredient is 1-99% in this sterilant component.Comprise also in this fungicide compsn that agricultural goes up acceptable carrier.
General formula (I of the present invention; II) compound and can process several formulations as the fungicide compsn of active ingredient and use, especially general formula (II) can directly be made into aqua and use; Both reduced with an organic solvent the pollution of environment, be more conducive to absorption and the conduction of plant again.In these compsns, also can add the liquid or solid carrier, and add an amount of tensio-active agent and come compounding application.
Other embodiment of the present invention is the method for control germ, and this method comprises compound of the present invention and compsn thereof are applied on the surface of said plant or its growth medium.Amount of application is generally per hectare 50 and restrains 500 grams, and preferred significant quantity is that per hectare 50 restrains 300 grams.In addition, also can add one or more other microbiocidal agent in compound of the present invention and in the active composition, can produce thus more efficient, the effect of wide spectrum.
(I, II) compound both can use separately as plant activation antiviral agents and also can cooperate other known sterilant, sterilant, plant-growth regulator or fertilizer to be mixed together use general formula of the present invention.
Should be clear and definite be in claim scope of the present invention, can carry out various changes and conversion as required.
Embodiment
The following example is tested the plant activation anti-disease activity that the result can further be used for explaining compound of the present invention with giving birth to test, but does not mean that restriction the present invention.
Synthetic embodiment
Synthesizing of compound 1
1, the preparation of benzo [1,2,3]-thiadiazoles-7 formyl chloride
1.80 gram (0.01 mole) benzo [1,2,3]-thiadiazoles-7-formic acid and 10 milliliters of thionyl chlorides are joined in 50 milliliters of round-bottomed flasks; Reflux is 8 hours under 80～90 degree, and decompression steams excessive thionyl chloride, gets pale brown look solid; Midbody benzo [1; 2,3]-and the sealing of thiadiazoles-7-formyl chloride is kept in the vacuum drier subsequent usely, and the consumption of this compound can or dwindle by the expansion of corresponding proportion.
2, compound 1: benzo [1,2,3]-thiadiazoles-7-carboxylic acid (N, N-dimethyl-) ethyl ester synthetic
In 100 milliliters of round-bottomed flasks, add good benzo [1,2, the 3]-thiadiazoles of prepared beforehand-7-formyl chloride 3.60 grams (0.02 mole); 40 milliliters of methylene dichloride of handling, induction stirring slowly drip the N of 1.5 grams (0.02 mole) for a moment then under ice bath; The N-dimethyl ethanol, the mixed solution of 3.0 milliliters triethylamine and 20 milliliters of methylene dichloride drips off the back stirred overnight at room temperature; To give a baby a bath on the third day after its birth with 30 ml waters after reaction finishes inferior at every turn, and organic layer anhydrous sodium sulfate drying 4 hours, precipitation get 3.75 gram brown liquids; Thick productive rate 79.1%, 200～300 order silica gel column chromatographies (eluent is the sherwood oil of 60～90 degree: ETHYLE ACETATE volume ratio 3: 1 adds a little triethylamine in the eluent); Get pure article 2.3 grams of weak yellow liquid, clean productive rate 48.5%; Results of elemental analyses (measured value/theoretical value): C:50.60/50.62, H:4.65/4.67, N:17.74/17.71,
O:13.52/13.49, S:13.49/13.51MS (m/z): 238.05 (M+1); H
1NMR (solvent: CDCl
3, chemical shift): 8.012 (1H, d, J=8.5Hz, CH), 7.612 (1H, d, J=7.5Hz, CH), 7.412 (1H, q, J=8.5Hz, J=7.5Hz, CH), 5.680 (2H, s, CH2), 2.355 (6H, s, C H
3), the results of elemental analyses of this compound in the limit of error that allows, H
1NMR, MS data presentation and its chemical structure are consistent.
Synthesizing of compound 2
In 100 milliliters of round-bottomed flasks, add good benzo [1,2, the 3]-thiadiazoles of prepared beforehand-7-formyl chloride 3.60 grams (0.02 mole); 40 milliliters of methylene dichloride of handling, induction stirring slowly drip the 1-[N of 2.34 grams (0.02 mole) for a moment then under ice bath; The N-diethylammonium] ethanol, the mixed solution of 3.0 milliliters triethylamine and 20 milliliters of methylene dichloride drips off the back stirred overnight at room temperature; To give a baby a bath on the third day after its birth with 30 ml waters after reaction finishes inferior at every turn, and organic layer anhydrous sodium sulfate drying 4 hours, precipitation get 4.15 gram brown liquids; Thick productive rate 74.3%, 200～300 order silica gel column chromatographies (eluent is the sherwood oil of 60～90 degree: ETHYLE ACETATE volume ratio 2: 1 adds a little triethylamine in the eluent); Get pure article 2.3 grams of weak yellow liquid, clean productive rate 41.2%; Results of elemental analyses (measured value/theoretical value): C:55.87/55.89, H:6.15/6.13, N:15.08/15.04, O:11.46/11.45, S:11.51/11.48; MS (m/z): 280.36 (M+1); HNMR (solvent: CDCl
3, chemical shift): 8.012 (1H, d, J=8.5Hz, CH), 7.612 (1H, d, J=7.5Hz, CH), 7.412 (1H, q, J=8.5Hz, J=7.5Hz, CH), 5.080 (1H, q, J=7.5Hz, CH), 1.650 (3H, d, J=7.5Hz, CH
3), 2.355 (4H, q, J=6.5Hz, CH
2), 1.355 (6H, t, J=6.5Hz, CH
3).
Synthesizing of compound 17
In 100 milliliters of round-bottomed flasks, add good benzo [1,2, the 3]-thiadiazoles of prepared beforehand-7-formyl chloride 3.60 grams (0.02 mole); 40 milliliters of methylene dichloride of handling, induction stirring slowly drip the N of 2.88 grams (0.02 mole) for a moment then under ice bath; The N-diisopropyl ethylenediamine, the mixed solution of 3.0 milliliters triethylamine and 20 milliliters of methylene dichloride drips off the back stirred overnight at room temperature; To give a baby a bath on the third day after its birth with 30 ml waters after reaction finishes inferior at every turn, and organic layer anhydrous sodium sulfate drying 4 hours, precipitation get 3.45 gram red-brown solids; Thick productive rate 56.4%, 200～300 order silica gel column chromatographies (eluent is the sherwood oil of 60～90 degree: ETHYLE ACETATE volume ratio 5: 1 adds a little triethylamine in the eluent); Get pure article 1.8 grams of white solid, mp:102 ℃, clean productive rate 29.4%; Results of elemental analyses (measured value/theoretical value): C:58.75/58.79, H:7.25/7.24, N:18.29/18.28,0:5.20/5.22, S:10.50/10.46; MS (m/z): 307.43 (M+1); HNMR (solvent: CDCl
3, chemical shift): 8.112 (1H, d, J=8.9Hz, CH), 7.612 (1H, d, J=7.8Hz, CH), 7.545 (1H, q, J=8.9Hz, J=7.8Hz, CH), 3.380 (2H, t, J=7.7Hz, CH
2), 2.650 (2H, t, J=7.7Hz, CH
2), 2.980 (2H, q, J=7.8Hz, CH), 1.055 (12H, d, J=7.8Hz, CH
3).
Compound 1-H's is synthetic
In the four-hole round-bottomed flask of 25mL, add 2 '-N, N-dimethyl--benzo [1; 2,3]-and methylene dichloride that thiadiazoles-7-ethyl formate 0.251g (0.001mol) and 10ml handled, induction stirring is for a moment; Under ice bath, slowly feed exsiccant HCl gas then, TLC detects and only needs logical 0.5h to react to finish, so stopped reaction; Transfer to reaction solution in the round-bottomed flask of 50ml then, get white solid compound 1-H, 0.2875g with the Rotary Evaporators precipitation; Yield 100%, this solid are exposed in the air nonhygroscopic and soluble in water.mp?205～207℃；
1H?NMR(400MHz，D
2O)δ：2.99(s，6H，C
H 3)，3.67-3.69(m，2H，C
H 2)，4.74-4.79(m，2H，C
H 2)，7.68(dd，1H，J
H＝6.8Hz，J
H＝8.4Hz，Ar
H)，8.25(d，1H，J
H＝6.8Hz，Ar
H)，8.65(d，1H，J
H＝8.4Hz，Ar
H)；HRMS：calc?for?C
11H
14N
3O
2SCl；M252.0801；found?252.0810。
Compound 2-H's is synthetic
Compound method is synthetic with compound compound 1-H's, obtains white solid compound 2-H, and yield 100%, this solid are exposed in the air nonhygroscopic and soluble in water.mp?179～180℃；
1H?NMR(400MHz，D
2O)δ：1.32(t，6H，J
H＝7.2Hz，C
H 3)，3.34(q，4H，J
H＝7.2Hz，C
H 2)，3.68(t，2H，J
H＝4.8Hz，C
H 2)，4.72(t，2H，J
H＝4.8Hz，C
H 2)，7.60(dd，1H，J
H＝6.8Hz，J
H＝8.4Hz，Ar
H)，8.10(d，1H，J
H＝6.8Hz，Ar
H)，8.54(d，1H，J
H＝8.4Hz，Ar
H)；HRMS：calc?for?C
13H
18N
3O
2SCl；M
+280.1114；found?280.1121。
Compound 3-H is synthetic
Compound method is synthetic with compound 1-H's, obtains white solid compound 3-H, and yield 100%, this solid are exposed in the air nonhygroscopic and soluble in water.mp?153～156℃；
1H?NMR(400MHz，D
2O)δ：1.36-1.39(m，12H，C
H 3)，3.77-3.84(m，2H，C
H)，3.66(t，2H，J
H＝4.8Hz，C
H 2)，4.73(t，2H，J
H＝4.8Hz，C
H 2)，8.22(dd，1H，J
H＝7.2Hz，J
H＝16.0Hz，Ar
H)，8.22(d，1H，J
H＝7.2Hz，Ar
H)，8.68(d，1H，J
H＝16.0Hz，Ar
H)；?HRMS：calc?for?C
15H
22N
3O
2SCl；M
+308.1427；found?308.1429。
Other compound all can obtain through similar approach in table 1, the table 2.
Give birth to and survey instance:
For new synthetic diazosulfide and 4-methyl isophthalic acid; 2; The biological activity of 3-thiadiazoles derivative has only been tested infecting the anti-intensity that lures of botrytis cinerea (Botrytis cinerea per.), and the preparation of these two serial target compound medicaments all is to be that biological activity test is direct water-soluble test through adding directly that water processes; Wherein 2% kasugamycin wettable powder is the contrast medicament, and botrytis cinerea liquid is only inoculated in the clear water contrast.
Target compound to the concrete TP of the prophylaxis effect of graw mold of tomato is: tomato seedling 4～5 leaves of selecting uniformity; Adopt air to connect and blow spray painting head spray liquid; Leave dual sides evenly is sprayed onto; Treat the soup seasoning, behind 48h, adopt hand-held plastics atomizer that the blade tow sides are evenly sprayed botrytis cinerea liquid.When spraying medicine (bacterium) liquid, be covered with the blade face pros and cons but do not drip with droplet and be advisable.After the inoculation plant is placed 25 ℃, relative humidity is in 90% the environment greenhouse of preserving moisture.Inoculate 8 days " Invest, Then Investigate "s and all inoculate the disease index of blade.
0 grade: no scab; 1 grade: lesion area accounts for below 5% of whole leaf area; 3 grades: lesion area accounts for 6～10% of whole leaf area; 5 grades: lesion area accounts for 11～25% of whole leaf area; 7 grades: lesion area accounts for 26～50% of whole leaf area; 9 grades: lesion area accounts for more than 50% of whole leaf area;
Disease index=∑ (the sick number of sheets * relative progression) * 100/ (investigating total number of sheets * 9)
Control effect (%)=(the contrast disease refers to-handle that disease refers to) * 100/ contrast disease refers to
General formula I I compound directly adds water, does not add any tensio-active agent and auxiliary agent, is made into aqua and lures the activity resistent test.
Part of compounds test result such as following table:
Diazosulfide series of parts compound is to luring the activity resistent result in seedling stage of graw mold of tomato
Z
5*: benzo [1,2,3]-thiadiazoles-7-formic acid;
Z
7*: benzo [1,2,3] thiadiazoles-7-carboxylic acid first thioesters (BTH) * * contrasts medicament.
Claims (5)
1. benzo [2,3]-thiadiazoles-7-ramification of carboxylic esters and salt thereof, as general formula (I, II) shown in:
Wherein:
X represention oxygen atom, nitrogen-atoms, sulphur atom; N=0,1,2,3,4,5 ... Or (CH
2)
nRepresentative has the alkyl of side chain; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, or other negative ions.R
1Represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl or the aryl of a 1-6 carbon atom; R
2Represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl or the aryl of a 1-6 carbon atom; Or R
1, R
2Be selected from following structure:
2. compound as claimed in claim 1 is characterized in that, general formula (I, II) in:
N=1～4; X represents N, O, S; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, or other negative ions; R
1, R
2Be selected from H, C
1-C
4Alkyl or R
1=R
2Be selected from following structure:
3. the described compound of claim 1 or its compsn are used for the purposes of activated plant self disease-resistant performance and prevention and controlling plant disease.
4. a fungicide mixture contains compound as claimed in claim 1 and goes up acceptable carrier with agricultural, and the weight percentage of active ingredient is 1-99% in the compsn.
5. the method for a controlling plant disease is characterized in that: to the fungicide mixture as claimed in claim 4 of plant seed and foliage applying significant quantity.
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| WO2017017626A1 (en) * | 2015-07-28 | 2017-02-02 | Adam Mickiewicz University Foundation | Application of 7-carboxybenzo[1,2,3]thiadiazole amides as plant stimulants |
| CN109674806A (en) * | 2019-01-14 | 2019-04-26 | 福州奥尼多生物科技有限公司 | Purposes of the kasugarnycin in preparation antibacterials |
| CN113200933A (en) * | 2021-05-19 | 2021-08-03 | 河南师范大学 | Method for synthesizing optically active benzocarboxylate compound by asymmetric addition reaction |
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| CN103333113B (en) * | 2013-06-14 | 2018-09-28 | 南开大学 | The preparation and application study of fluxapyroxad like derivatives |
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