CN110183428B - Furan thiocarbamate compound containing 1,2,3, 4-tetrazole and preparation method and application thereof - Google Patents
Furan thiocarbamate compound containing 1,2,3, 4-tetrazole and preparation method and application thereof Download PDFInfo
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Abstract
The invention disclosesA furan thiocarbamate compound containing 1,2,3, 4-tetrazole and a preparation method and application thereof are provided. The structure of the compound is as shown in a formula (III); wherein R is selected from hydrogen, halogen, nitro, hydroxyl and C1～4Alkyl radical, C1～4Haloalkyl, C1～4Alkoxy or C1～4One or more of haloalkyl groups. The structure of the compound contains a tetrazole heterocyclic structure and a 5-phenyl-2-furan ring structure, the structure is novel, the compound has good inhibition effect on Xanthomonas oryzae pv. oryzae and/or Xanthomonas oryzae x. oryzae pv. oryzae, and IC (integrated Circuit) of the compound50The value is even obviously lower than that of bismerthiazol and thiabendazole, is reduced by 18-25 times, has great application prospect in preventing and treating plant diseases caused by the two pathogenic bacteria, and can be prepared into a plant bactericide for application; meanwhile, the preparation method of the compound is simple and rapid, has high yield and is convenient for mass preparation.
Description
Technical Field
The invention belongs to the application field of heterocyclic compounds, and particularly relates to a furan thiocarbamate compound containing 1,2,3, 4-tetrazole as well as a preparation method and application thereof.
Background
Tetrazole heterocyclic compounds are five-membered aromatic heterocyclic compounds containing four nitrogen atoms, which are extremely important intermediates in organic synthesis and can be used for synthesizing products used in the fields of medicines, pesticides, industry and the like.
Among azole pesticides, herbicides of the sulfotetrazolium class, tetrazolinone class, plant growth regulators of the triazole methylthiotetrazole class having a significant effect on monocotyledons, fungicides such as simeconazole and benomyl, and insecticides such as fipronil and triazophos are currently available, have the advantages of high efficiency, low toxicity and safety to humans and animals, and are widely used in agricultural production ((a) Feng, g. -r.; Huo, a. -x.; Zhang, s. -x.; Wang, h. -q.j. nanjing Normal Univ. (nat. sci. ed.)2007,30,71.(b) Li, w.; Zhang, y. -m.; Wei. med, t.; ga., l. -m.j.org.chem.2008, 28,454, Yang. (c) luong., Yang. p.; green. 52. org g.31.35. chem. (g.). 52. biol.). biol.
In recent years, tetrazole heterocyclic compounds have more and more occupied positions in the creation of novel efficient environment-friendly pesticides, and in order to find compounds with novel structures and biological activities, designing and synthesizing various tetrazole heterocyclic compounds is a very important approach.
Disclosure of Invention
The invention aims to provide a furan thiocarbamate compound containing 1,2,3, 4-tetrazole. The structure of the compound contains a tetrazole heterocyclic structure and a 5-phenyl-2-furan ring structure, the structure is novel, the compound has good inhibition effect on Xanthomonas oryzae pv. oryzae and/or Xanthomonas oryzae x. oryzae pv. oryzae, and IC of the compound50The value is even obviously lower than that of bismerthiazol and thiabendazole, and the bactericidal composition has great application prospect in preventing and treating plant diseases caused by the two pathogenic bacteria and can be prepared into a plant bactericide for application.
The invention also aims to provide a preparation method of the furan thiocarbamate compound containing 1,2,3, 4-tetrazole.
The invention further aims to provide application of the furan thiocarbamate compound containing 1,2,3, 4-tetrazole.
The above object of the present invention is achieved by the following scheme:
a furan thiocarbamate compound containing 1,2,3, 4-tetrazole is disclosed as a formula (III):
wherein R is selected from hydrogen, halogen, nitro, hydroxyl and C1～4Alkyl radical, C1～4Haloalkyl, C1～4Alkoxy or C1～4One or more of haloalkyl groups.
Preferably, R is selected from one or more of hydrogen, fluoro, chloro, bromo, nitro, hydroxy, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, trifluoromethyl, trifluoromethoxy or trifluoroethyl.
Preferably, R is selected from hydrogen, 2-nitro, 3-nitro, 4-nitro, 2-fluoro, 3-fluoro, 4-fluoro, 2-bromo, 3-bromo, 4-bromo, 2-chloro, 3-chloro, 4-chloro, 2, 4-difluoro, 2, 6-difluoro, 2-methyl, 3-methyl, 4-methyl, 2-methoxy, 3-methoxy, 4-methoxy, 2-trifluoromethyl, 3-trifluoromethyl or 4-trifluoromethyl. The structure is one of the following structures:
more preferably, R is selected from 2-fluoro, 4-bromo, 2-chloro, 3-chloro, 4-chloro, 2, 4-difluoro or 2, 6-difluoro. The structure is one of the following structures:
more preferably, said R is selected from 4-chloro, 4-fluoro or 2, 4-difluoro. The structure is one of the following structures:
the invention also provides a preparation method of the furan thiocarbamate compound containing 1,2,3, 4-tetrazole, which comprises the following steps:
s1, in the presence of a diluent, reacting a compound shown as a formula I with SOCl2Reacting under the condition of heating reflux to prepare a compound shown in a formula II;
s2, in the presence of a diluent and inorganic base, N-methyl-5-mercapto-1, 2,3, 4-tetrazole is changed into sulfur negative ions under normal temperature stirring, and then the sulfur negative ions react with the compound shown in the formula (II) to prepare the target compound shown in the formula (III):
preferably, in the step S1, the reflux temperature is 80-120 ℃; the reflux time is 3-6 h; more preferably, the temperature of the reflux is 80-90 ℃; the reflux time is 3-4 h.
Preferably, in the step S2, the reaction temperature is 20-30 ℃; the reaction time is 0.5-1 h.
Preferably, in step S2, the diluent is selected from one or more of benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, acetone, butanone, methyl isobutyl ketone, acetonitrile, propionitrile, butyronitrile, N-dimethylformamide, N-dimethylacetamide, N-methyl-formanilide, N-methylpyrrolidone, hexamethylphosphoric triamide, methyl acetate, ethyl acetate, dimethyl sulfoxide, methanol, ethanol, N-propanol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether.
More preferably, the diluent is selected from one or more of acetonitrile, acetone or tetrahydrofuran.
Preferably, the inorganic base is selected from one or more of sodium hydroxide, potassium carbonate, sodium ethoxide, sodium bicarbonate or potassium acetate.
More preferably, the inorganic base is one or both of sodium hydroxide or potassium carbonate.
Preferably, in step S2, the amount ratio of the diluent, the compound represented by formula (ii), N-methyl-5-mercapto-1, 2,3, 4-tetrazole, and the inorganic base is 300-600: 1-2: 1-1.5: 1-3.
More preferably, the amount ratio of the diluent, the compound shown in the formula (II), and the N-methyl-5-mercapto-1, 2,3, 4-tetrazole to the inorganic base is 400:1:1: 2.
The application of the furan thiocarbamate compound containing 1,2,3, 4-tetrazole in preparing the plant disease control medicine is also within the protection scope of the invention.
Preferably, the plant disease control drug is a plant disease bactericide.
More preferably, the plant disease fungicide is a plant disease caused by pathogenic bacteria of Xanthomonas oryzae pv. oryzae and/or Xanthomonas oryzae x. oryzae pv. oryzae.
Compared with the prior art, the invention has the following beneficial effects:
the structure of the compound contains a tetrazole heterocyclic structure and a 5-phenyl-2-furan ring structure, the structure is novel, the compound has good inhibition effect on Xanthomonas oryzae pv. oryzae and/or Xanthomonas oryzae x. oryzae pv. oryzae, and IC of the compound50The value is even obviously lower than that of bismerthiazol and thiabendazole, is reduced by 18-25 times, has great application prospect in preventing and treating plant diseases caused by the two pathogenic bacteria, and can be prepared into a plant bactericide for application;
meanwhile, the preparation method of the compound is simple and rapid, has high yield and is convenient for large-batch preparation in the actual production process.
Detailed Description
The present invention is further described in detail below with reference to specific examples, which are provided for illustration only and are not intended to limit the scope of the present invention. The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.
EXAMPLE 1 Synthesis of Compound III-1
The specific preparation process of the compound III-1 is as follows:
0.44g of 5- (2-chlorophenyl) -2-furancarboxylic acid (2.0mmol) and 5mL of thionyl chloride are sequentially added into a 50mL single-neck flask; heating and refluxing for 3 hours, stopping heating, cooling the reaction liquid to room temperature, and removing the residual thionyl chloride by reduced pressure distillation to obtain a furoyl chloride intermediate which is directly used in the next step without purification;
adding 0.12g (2.0mmol) of N-methyl-5-mercapto-1, 2,3, 4-tetrazole, 0.55g of potassium carbonate (4.0mmol) and 20mL of acetonitrile into a 50mL single-neck bottle, and stirring at normal temperature for 0.5 h; dripping acetonitrile solution of furoyl chloride at room temperature, and reacting at room temperature for 1h after dripping is finished; monitoring by Thin Layer Chromatography (TLC), after the reaction is finished, filtering the reaction solution, spin-drying the filtrate to obtain a brown crude product, and separating and purifying the crude product by silica gel column chromatography (dichloromethane/V: methanol/V ═ 100:1) to obtain 0.519g of a light yellow solid compound, wherein the yield is as follows: 81 percent.1H NMR(400MHz,Chloroform-d)δ7.98(dd,J＝7.7,1.8Hz,1H),7.53(dd,J＝7.9,1.4Hz,1H),7.49(d,J＝3.9Hz,1H),7.46–7.38(m,2H),7.36(d,J＝3.9Hz,1H),4.13(s,3H).
The structure of compound III-1 was identified as follows:
EXAMPLE 2 Synthesis of Compound III-2
The procedure is as in example 1, except that 5- (3-fluorophenyl) -2-furoyl chloride is used instead of 5- (2-chlorophenyl) -2-furoyl chloride, and a dark yellow solid III-2 is obtained.
1H NMR(400MHz,Chloroform-d)δ7.79(q,J＝1.4Hz,1H),7.73–7.68(m,1H),7.47(d,J＝3.8Hz,1H),7.44–7.40(m,2H),6.94(d,J＝3.8Hz,1H),4.13(s,3H).
EXAMPLE 3 Synthesis of Compound III-3
The procedure is as in example 1, except that 5- (4-chlorophenyl) -2-furoyl chloride is used instead of 5- (2-chlorophenyl) -2-furoyl chloride, and light yellow solid III-3 is obtained.
1H NMR(400MHz,Chloroform-d)δ7.76(d,J＝8.6Hz,2H),7.51–7.42(m,3H),6.90(d,J＝3.8Hz,1H),4.13(s,3H).
Example 4: synthesis of Compound III-4
The procedure is as in example 1, except that 5- (2-fluorophenyl) -2-furoyl chloride is used instead of 5- (2-chlorophenyl) -2-furoyl chloride, and a white solid III-4 is obtained.
1H NMR(400MHz,Chloroform-d)δ7.99(td,J＝7.7,1.5Hz,1H),7.49(d,J＝3.8Hz,1H),7.48–7.40(m,1H),7.34–7.29(m,1H),7.22(dd,J＝10.9,8.6Hz,1H),7.09(t,J＝3.6Hz,1H),4.13(s,3H).
EXAMPLE 5 Synthesis of Compound III-5
The procedure is as in example 1, except that 5- (3-fluorophenyl) -2-furoyl chloride is used instead of 5- (2-chlorophenyl) -2-furoyl chloride, and yellow solid III-5 is obtained.
1H NMR(400MHz,Chloroform-d)δ7.63–7.59(m,1H),7.54–7.44(m,3H),7.15(tdd,J＝8.4,2.6,0.9Hz,1H),6.94(d,J＝3.8Hz,1H),4.13(s,3H).
Example 6: synthesis of Compound III-6
The procedure is as in example 1, except that 5- (4-fluorophenyl) -2-furoyl chloride is used instead of 5- (2-chlorophenyl) -2-furoyl chloride, and light yellow solid III-6 is obtained.
1H NMR(400MHz,Chloroform-d)δ7.87–7.78(m,2H),7.47(d,J＝3.8Hz,1H),7.23–7.14(m,2H),6.86(d,J＝3.8Hz,1H),4.13(s,3H).
EXAMPLE 7 Synthesis of Compound III-7
The procedure is as in example 1, except that 5- (2, 4-difluorophenyl) -2-furoyl chloride is used instead of 5- (2-chlorophenyl) -2-furoyl chloride, and light yellow solid III-7 is obtained.
1H NMR(400MHz,Chloroform-d)δ7.98(td,J＝8.6,6.3Hz,1H),7.49(d,J＝3.8Hz,1H),7.13–6.91(m,3H),4.13(s,3H).
EXAMPLE 8 Synthesis of Compound III-8
The procedure is as in example 1, except that 5- (2, 6-difluorophenyl) -2-furoyl chloride is used instead of 5- (2-chlorophenyl) -2-furoyl chloride, and a brown solid III-8 is obtained.
1H NMR(600MHz,Chloroform-d)δ7.47(d,J＝3.8Hz,1H),7.44–7.39(m,1H),7.10–7.05(m,3H),4.12(s,3H).
EXAMPLE 9 Synthesis of Compound III-9
The procedure is as in example 1, except that 5- (2-nitrophenyl) -2-furoyl chloride is used instead of 5- (2-chlorophenyl) -2-furoyl chloride, and a pale white solid III-9 is obtained.
1H NMR(400MHz,Chloroform-d)δ7.90(dd,J＝8.1,1.1Hz,1H),7.82(dd,J＝7.8,1.4Hz,1H),7.74(td,J＝7.6,1.3Hz,1H),7.65(td,J＝7.8,1.5Hz,1H),7.45(d,J＝3.8Hz,1H),6.89(d,J＝3.8Hz,1H),4.12(s,3H).
EXAMPLE 10 Synthesis of Compounds III-10
The procedure is as in example 1, except that 5- (3-nitrophenyl) -2-furoyl chloride is used instead of 5- (2-chlorophenyl) -2-furoyl chloride, and a yellow solid III-10 is obtained.
1H NMR(400MHz,Chloroform-d)δ8.64(t,J＝1.9Hz,1H),8.30(ddd,J＝8.2,2.2,1.0Hz,1H),8.20–8.13(m,1H),7.72(t,J＝8.0Hz,1H),7.52(d,J＝3.8Hz,1H),7.08(s,1H).
EXAMPLE 11 Synthesis of Compound III-11
The procedure is as in example 1, except that 5- (4-nitrophenyl) -2-furoyl chloride is used instead of 5- (2-chlorophenyl) -2-furoyl chloride, and a pale yellow solid III-11 is obtained.
1H NMR(400MHz,Chloroform-d)δ8.39–8.32(m,2H),8.02–7.96(m,2H),7.51(d,J＝3.9Hz,1H),7.12(d,J＝3.8Hz,1H),4.14(s,3H).
EXAMPLE 12 Synthesis of Compounds III-12
The procedure is as in example 1, except that 5- (4-bromophenyl) -2-furoyl chloride is used instead of 5- (2-chlorophenyl) -2-furoyl chloride, and light yellow solid III-12 is obtained.
1H NMR(400MHz,Chloroform-d)δ7.72–7.66(m,2H),7.65–7.60(m,2H),7.47(d,J＝3.8Hz,1H),6.92(d,J＝3.8Hz,1H),4.13(s,3H).
EXAMPLE 13 Synthesis of Compounds III-13
The procedure is as in example 1, except that 5- (4-methylphenyl) -2-furoyl chloride is used instead of 5- (2-chlorophenyl) -2-furoyl chloride, and light yellow solid III-13 is obtained.
1H NMR(400MHz,Chloroform-d)δ7.72(d,J＝8.2Hz,2H),7.45(d,J＝3.8Hz,1H),7.29(d,J＝8.0Hz,2H),6.86(d,J＝3.8Hz,1H),4.12(s,3H),2.42(s,3H).
EXAMPLE 14 Synthesis of Compounds III-14
The procedure is as in example 1, except that 5- (4-methoxyphenyl) -2-furoyl chloride is used instead of 5- (2-chlorophenyl) -2-furoyl chloride, and yellow solid III-14 is obtained.
1H NMR(600MHz,Chloroform-d)δ7.79–7.74(m,2H),7.44(d,J＝3.8Hz,1H),7.01–6.97(m,2H),6.78(d,J＝3.8Hz,1H),4.11(s,3H),3.87(s,3H).
EXAMPLE 15 Synthesis of Compounds III-15
The procedure is as in example 1, except that 5-phenyl-2-furoyl chloride is used instead of 5- (2-chlorophenyl) -2-furoyl chloride, and a yellow solid III-15 is obtained.
1H NMR(600MHz,Chloroform-d)δ7.85–7.81(m,1H),7.70–7.67(m,2H),7.65–7.60(m,2H),7.52–7.48(m,1H),7.46(d,J＝3.8Hz,1H),6.91(d,J＝3.8Hz,1H),4.12(s,3H).
The structures, appearances, mass spectra and elemental analysis results of compounds III-1 to III-15 are shown in Table 1.
TABLE 1 Structure, appearance, Mass Spectrometry and elemental analysis results of Compounds III-1 to III-15
EXAMPLE 16 fungicidal Activity of Compounds III-1 to III-15
The employed pathogenic bacteria were rice bacterial blight (Xoo) and rice bacterial streak disease (Xoc). The pathogenic bacteria used in the test are all sampled from the diseased parts of field crops, greenhouse vegetables and stored fruits, the pathogens are collected from the diseased parts, and are inoculated and purified on corresponding culture media, and the pathogens are identified as rice bacterial blight bacteria Xoo (Xanthomonas oryzae pv. oryzae) and rice bacterial streak bacteria Xoc (X. oryzae pv. oryzae Zicola).
(1) Fungicidal Activity of test Compounds against Paddy Rice Blakeslea Blume (Xoo)
Test concentrations of compounds: dissolving the compound to be tested, the bismerthiazol serving as a control bactericide and the thiodiazole copper serving as a control bactericide in DMSO respectively, and diluting the solution to 200 mu g/mL by using a sterile aqueous solution of 0.1% Tween 20-1And 100. mu.g.mL-1. The test strain was rice bacterial blight (Xanthomonas oryzae pv. oryzae).
Screening assays for in vitro bactericidal activity were performed on Xoo (xanthomas oryzae pv. oryzae) using turbidimetry for 15 compounds in table 1, compounds iii-1 to iii-15: 1mL of sample solution to be detected and 40 mu L of culture solution containing Xoo thallus are added into 4mL of NB liquid culture medium, and the mixture is cultured for 36-48 hours at the temperature of 28 ℃ at 180 r/min. The OD (OD) values of the bacterial solutions of the respective concentrations were measured on a microplate reader595) DMSO was used as negative control. The formula for calculating the bacteriostasis rate is as follows:
inhibition (%) (blank group)OD595Experimental group OD595) Blank OD595×100
Each concentration of each compound was tested in triplicate and the results are shown in Table 2, and then the EC of the compound on Xoo was tested by adjusting the concentration gradient of the compound based on the results50The values, the results of the measurements are shown in Table 2.
Analyzing and evaluating the measured data by using a Logistic model, and analyzing by using a statistical data analysis processing system to obtain the EC of the target compound on the Xoo50The values and results are shown in Table 2.
TABLE 2 in vitro antibacterial Activity of Compounds on Xoo
As can be seen from Table 2, the bactericidal activity of the compounds III-1 to III-15 on Xoo is higher than that of bismerthiazol and thiodiazole copper, wherein the compounds III-1, III-3, III-4, III-6, III-7 and III-8 show the hundred percent of antibacterial activity at the concentration of 200 mu g/mL, and the compounds III-3, III-6 and III-7 still show the hundred percent of inhibition rate at the concentration of 100 mu g/mL. Median inhibitory concentration (EC)50) All the compounds show that the bacteriostatic activity is better than that of bismerthiazol (94.35 +/-1.95 mu g/mL) and thiabendazole (124.83 +/-3.66 mu g/mL); wherein, the compounds III-3 (4.83 +/-0.52 mu g/mL), III-6 (5.83 +/-0.66 mu g/mL) and III-7 (6.35 +/-0.81 mu g/mL) show obvious bacteriostatic activity, and the EC thereof50Compared with bismerthiazol and thiabendazole, the value is reduced by 18-25 times.
From the structure and activity data of the compounds in the table 2, the introduction of electron-withdrawing groups (such as chlorine and fluorine) on the benzene ring is beneficial to the activity of the compounds, and the bacteriostatic activity of the compounds is improved; the introduction of electron-donating groups (such as methyl and methoxy) is not beneficial to the improvement of the bacteriostatic activity; meanwhile, when the same substituent is substituted at different positions on a benzene ring, the activity of the compound is also influenced, wherein the substitution positions on the benzene ring are arranged in sequence according to the activity: para > ortho > meta.
(2) Activity of test compounds against bacterial leaf streak disease of rice (Xoc).
Test concentrations of compounds: dissolving the compound to be tested and control bactericides bismerthiazol and thiediazole copper in DMSO, and diluting to 200 mu g/mL and 100 mu g/mL by using a sterile aqueous solution of 0.1% Tween 20; the test strain was rice bacterial streak germ Xoc (X. oryzae pv. oryzae).
Screening assays for in vitro bactericidal activity were performed on 15 compounds in table 1, compounds iii-1 to iii-15, using turbidimetry against Xoc (x. oryzae pv. oryzae). 1mL of sample solution to be tested and 40. mu.L of culture solution containing Xoc cells are added into 4mL of NB liquid culture medium, and cultured for 36-48 hours at the temperature of 28 ℃ at 180 r/min. The OD (OD) values of the bacterial solutions of the respective concentrations were measured on a microplate reader595) DMSO was used as a blank control. The formula for calculating the bacteriostasis rate is as follows:
inhibition (%) (blank OD)595Experimental group OD595) Blank OD595×100
Each concentration of each compound was tested in triplicate, and based on the resulting inhibition, the EC of Xoc for the target compound was analyzed using a statistical data analysis processing system using a Logistic model for evaluation50A value; the results are shown in Table 3.
Ex vivo antibacterial Activity of the Compounds of Table 3 against Xoc
As can be seen from Table 3, the in vitro bacteriostatic activity of the compounds III-1 to III-15 on Xoc is higher than that of bismerthiazol and copper thiediazole, wherein the compounds III-1, III-3, III-4, III-6, III-7 and III-8 show hundreds of percent of bacteriostatic activity at the concentration of 200 mu g/mL,at a concentration of 100. mu.g/mL, compounds III-3, III-6, III-7 still showed a hundred percent inhibition. Median inhibitory concentration (EC)50) All the compounds show that the bacteriostatic activity is better than that of bismerthiazol (166.78 +/-4.38 mu g/mL) and thiabendazole (254.76 +/-6.52 mu g/mL); wherein, the compounds III-3 (9.88 +/-0.73 mu g/mL), III-6 (12.67 +/-1.25 mu g/mL), III-7 (24.39 +/-1.26 mu g/mL) and III-8 (36.78 +/-2.03 mu g/mL) show obvious bacteriostatic activity, and the EC thereof50The value is reduced by 18-25 times compared with the values of bismerthiazol and thiabendazole.
From the structure and activity data of the compounds in table 3, the introduction of electron-withdrawing groups (such as chlorine and fluorine) on the benzene ring is beneficial to the activity of the compounds, and the biological activity of the compounds is improved; the introduction of electron-donating groups (such as methyl and methoxy) is not favorable for improving the activity of the compound; meanwhile, when the same substituent is substituted at different positions on a benzene ring, the activity of the compound is also influenced, wherein the substitution positions on the benzene ring are arranged in sequence according to the activity: para > ortho ≈ meta.
It should be finally noted that the above examples are only intended to illustrate the technical solutions of the present invention, and not to limit the scope of the present invention, and that other variations and modifications based on the above description and thought may be made by those skilled in the art, and that all embodiments need not be exhaustive. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (8)
1. A furan thiocarbamate compound containing 1,2,3, 4-tetrazole is characterized in that the structure of the compound is as shown in formula (III):
wherein R is selected from hydrogen, halogen, nitro, hydroxyl and C1～4Alkyl radical, C1～4Haloalkyl, C1～4One of alkoxy or trifluoromethoxy.
2. The 1,2,3, 4-tetrazole-containing furanthiocarbamate compound of claim 1, wherein R is one selected from hydrogen, fluorine, chlorine, bromine, nitro, hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, or trifluoroethyl.
3. The furan thiocarbamate compound containing 1,2,3, 4-tetrazole is characterized in that the structure is one of the following structures:
4. the 1,2,3, 4-tetrazole-containing furanthiocarbamate compound of claim 3, which is characterized in that the structure is one of the following structures:
5. the preparation method of the furan thiocarbamate compound containing 1,2,3, 4-tetrazole as claimed in claim 1 or 2, is characterized by comprising the following steps:
s1, in the presence of a diluent, reacting a compound shown as a formula I with SOCl2Reacting under the condition of heating reflux to prepare a compound shown in a formula II;
s2, in the presence of a diluent and inorganic base, N-methyl-5-mercapto-1, 2,3, 4-tetrazole is changed into sulfur negative ions under normal temperature stirring, and then the sulfur negative ions react with the compound shown in the formula (II) to prepare the target compound shown in the formula (III):
6. the preparation method of the 1,2,3, 4-tetrazole-containing furanthiocarbamate compound as claimed in claim 5, wherein in the step S1, the reflux temperature is 80-120 ℃; the reflux time is 3-6 h;
in the step S2, the reaction temperature is 20-30 ℃; the reaction time is 0.5-1 h;
in step S2, the diluent is selected from one or more of benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, acetone, butanone, methyl isobutyl ketone, acetonitrile, propionitrile, butyronitrile, N-dimethylformamide, N-dimethylacetamide, N-methyl-formanilide, N-methylpyrrolidone, hexamethylphosphoric triamide, methyl acetate, ethyl acetate, dimethyl sulfoxide, methanol, ethanol, N-propanol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether;
the inorganic base is selected from one or more of sodium hydroxide, potassium carbonate, sodium ethoxide, sodium bicarbonate or potassium acetate.
7. The use of furanthiocarbamate compounds containing 1,2,3, 4-tetrazole according to any one of claims 1 to 4 for preparing a medicament for controlling plant diseases, wherein the plant diseases are plant diseases caused by pathogenic bacteria of Xanthomonas oryzae pv. oryzae and/or Xanthomonas oryzae pv. oryzae.
8. The use according to claim 7, characterized in that the plant disease control drug is a plant disease bactericide.
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