CN105859645A - Halogen-substituted triazole compound with benzene rings, method for preparing halogen-substituted triazole compound and application thereof - Google Patents

Abstract

The invention discloses a halogen-substituted triazole compound with benzene rings, a method for preparing the halogen-substituted triazole compound and application thereof. The halogen-substituted triazole compound with the benzene rings is provided with a structure shown as a general formula I. An R in the general formula I represents hydrogen or halogen atoms or methoxy or ethoxy or benzyloxy or nitryl or dimethylamino; an X in the general formula I represents bromine atoms or chlorine atoms. The halogen-substituted triazole compound with the benzene rings, the method and the application have the advantages that the halogen-substituted triazole compound with the benzene rings is based on triazole ring skeletons, the halogen atoms are introduced into four bits of the triazole ring skelteons, the benzene rings or the benzene rings with substituents are introduced into five bits of the triazole ring skeletons, and accordingly the halogen-substituted triazole compound with the benzene rings can be obtained; the halogen-substituted triazole compound with the benzene rings is good in bactericidal activity for crop germs and can be used as a bactericide for the germs generated in crop growth procedures.

Description

A class of triazole compounds containing benzene ring and halogen substitution and its preparation method and use

technical field

The invention relates to the technical field of medicinal chemistry, in particular to a class of triazole compounds containing benzene rings and halogen substitutions, a preparation method and application thereof.

Background technique

Triazole compounds have a wide range of biological activities in pesticides and medicines. Among them, the chemical structure containing triazole and substituted benzene rings has been widely studied in the field of fungicides. Oxiconazole has been developed so far (The Pesticide Manual, 2003, 13, 43 ), furconazole (EP 258161), cyproconazole (US 4664696), diniconazole (US 4203995), flueconazole (US4464381), triconazole (US 4623654) etc. are effective against crop powdery mildew and scab , sheath blight and other fungicide varieties with good control effect. From the perspective of chemical structure, the above fungicides are all docked with the substituted benzene ring through 2-3 carbon bridges through the 1-position nitrogen atom of the 1,2,4-triazole ring, and through the 5-position carbon atom of the triazole ring There is no report on the antibacterial activity of compounds directly docked with benzene rings or substituted benzene rings.

Contents of the invention

The present invention aims to provide a triazole compound containing a benzene ring and a halogen substitution and a preparation method thereof, including its use for killing crop pathogens, so as to provide a class of triazole compounds containing a substituted benzene ring and a halogen substitution having bactericidal activity against crop pathogens. of triazole compounds.

In order to achieve the above object, the specific technical scheme is as follows:

The first aspect of the present invention provides a class of triazole compounds containing benzene rings and halogen substitutions. The triazole compounds containing benzene rings and halogen substitutions have a structure represented by the following general formula I:

In the general formula I, R is hydrogen, halogen atom, methoxy, ethoxy, benzyloxy, nitro or dimethylamino; X is bromine atom or chlorine atom.

Further, the above-mentioned triazole compounds containing benzene ring and halogen substitution are selected from the following compounds:

The second aspect of the present invention provides a method for preparing the above-mentioned triazole compound containing a benzene ring and a halogen substitution, by reacting the first compound represented by the general formula II with the second compound represented by the general formula III to obtain the benzene-containing Ring and halogen-substituted triazole compounds, the general formula II and the general formula III are as follows:

In said II, R is H, a halogen atom, methoxy, ethoxy, benzyloxy, nitro or dimethylamino;

In said III, X is Br or Cl.

Further, the preparation method of the above-mentioned triazole compound containing benzene ring and halogen substitution is:

When the second compound is N-bromosuccinimide, the specific preparation method is: using isopropyl acetate as a solvent, mixing the first compound and N-bromosuccinimide according to the ratio of the amount of substance 1: 1.2-1.5, under reflux conditions, react for 5-12 hours to obtain a triazole compound containing benzene ring and bromine substitution;

When the second compound is N-chlorosuccinimide, the specific preparation method is: using N,N-dimethylformamide as a solvent, mixing the first compound and N-chlorosuccinimide according to The ratio of the amount of substances is 1:1.2-1.5, the reaction temperature is 45-50°C, and the reaction is 5-12 hours to obtain the triazole compound containing benzene ring and chlorine substitution.

Further, the preparation method of the above-mentioned triazole compound containing a benzene ring and a halogen substitution is: when the second compound is N-bromosuccinimide, the specific preparation method is: using isopropyl acetate as a solvent, the The ratio of the first compound to N-bromosuccinimide is 1:1.5 according to the amount of substances, and under reflux conditions, react for 5 to 12 hours to obtain a triazole compound containing benzene ring and bromine substitution;

When the second compound is N-chlorosuccinimide, using N,N-dimethylformamide as a solvent, the ratio of the first compound to N-chlorosuccinimide according to the amount of substance is 1: 1.5, the reaction temperature is 45-50°C, the reaction is 5-12 hours, and the triazole compound containing benzene ring and chlorine substitution is obtained.

The third aspect of the present invention provides a kind of fungicide, the main active ingredient of which contains the above-mentioned triazole compound containing benzene ring and halogen substitution.

The fourth aspect of the present invention provides a kind of use of the above-mentioned benzene ring-containing and halogen-substituted triazole compound or the above-mentioned fungicide to inhibit and kill the pathogens produced during the growth of crops.

Further, the pathogens used in the above-mentioned application are Fusarium rubella wheat, Phytophthora capsici, Alternaria alternifolia, Botrytis cinerea, Rice sheath blight or Sclerotinia sclerotiorum.

Further, in the above application, when the pathogen is Gibberella tritici, the structure of the triazole compound containing benzene ring and halogen substitution is as follows:

When the pathogen is Phytophthora capsici, the structure of the triazole compound containing benzene ring and halogen substitution is as follows:

When the pathogen is Alternaria tabacum, the structure of the triazole compound containing benzene ring and halogen substitution is as follows:

When the pathogen is Botrytis cinerea, the structure of the triazole compound containing benzene ring and halogen substitution is as follows:

When the pathogen is rice sheath blight, the structure of the triazole compound containing benzene ring and halogen substitution is as follows:

When the pathogen is Sclerotinia sclerotiorum, the structure of the triazole compound containing benzene ring and halogen substitution is as follows:

The principle and advantages of the present invention are as follows: The technical scheme of the present invention is based on the triazole ring skeleton, introduces a halogen atom at its 4-position, and introduces a benzene ring or replaces a benzene ring at its 5-position, so as to obtain Substituted triazole compounds. The triazole compound containing benzene ring and halogen substitution has good bactericidal activity on crop germs, and can be used as a fungicide for germs produced during crop growth.

detailed description

In order to make the purpose, features and advantages of the present invention more obvious and understandable, the specific implementation of the present invention will be described in detail below in conjunction with specific examples. In the following description, many specific details are set forth in order to fully understand the present invention, but the present invention can be implemented in many other ways different from those described here, and those skilled in the art can do similar Modifications, and therefore the present invention is not limited to the specific examples disclosed below.

The invention provides a triazole compound containing a benzene ring and a halogen substitution, which has a structure represented by the following general formula I:

In the above general formula I, R is hydrogen, halogen atom, methoxy, ethoxy, benzyloxy, nitro or dimethylamino, and X is Br or Cl.

In the triazole compound containing benzene ring and halogen substitution provided by the present invention, a halogen atom is introduced at the 4-position of the triazole ring, and a benzene ring or a substituted benzene ring is introduced at the 5-position, the resulting benzene ring and halogen-containing The substituted triazole compounds have better fungicidal activity against crop pathogens.

The triazole compound containing benzene ring and halogen substitution of the present invention has the following chemical structure:

The above 17 different triazole compounds containing benzene ring and halogen substitution have good bactericidal activity on crop pathogens, and can be used as fungicides for pathogens produced during crop growth.

As a preferred synthesis scheme of the present invention, the triazole containing benzene ring and halogen substitution represented by the above general formula I is obtained by reacting the first compound represented by the general formula II with the second compound represented by the general formula III Compound, said general formula II and general formula III are as follows:

In the above general formula II, R is H, a halogen atom, methoxy, ethoxy, benzyloxy, nitro or dimethylamino; in the above general formula III, X is Br or Cl.

In the above preparation method, a preferred embodiment is: in the preparation of the bromine-substituted triazole compound, using isopropyl acetate (Isopropyl acetate) as a solvent, the first compound represented by the general formula II and The ratio of N-bromosuccinimide (NBS) represented by general formula III is 1: 1.2 to 1.5 according to the amount of substances, and the preferred ratio is 1: 1.5. Under reflux conditions, react for 5 to 12 hours to obtain The triazole compound containing benzene ring and bromine substitution; in the preparation of chlorine substitution triazole compound, using N,N-dimethylformamide (DMF) as solvent, the said compound represented by general formula II The ratio of the first compound to N-chlorosuccinimide (NCS) represented by general formula III is 1:1.2～1.5 according to the amount of substance, the preferred ratio is 1:1.5, and the reaction temperature is 45～50°C , and react for 5-12 hours to obtain the triazole compound containing benzene ring and chlorine substitution. Under this process condition, the triazole compound containing benzene ring and halogen substitution can be prepared with a medium or higher yield. The reaction formula of above-mentioned reaction is as follows:

The triazole compound containing benzene ring and halogen substitution obtained by the above preparation method is usually a crude product of triazole compound containing benzene ring and halogen substitution. The crude product of the triazole compound adopts the mixed solution of petroleum ether and ethyl acetate (V _{petroleum ether} : V _{ethyl acetate} = 10: 1) as the eluent, and the triazole compound containing benzene ring and bromine can be obtained through silica gel column chromatography. The pure product of the azole compound; the crude product of the triazole compound containing a benzene ring and a chlorine substitution in the N,N-dimethylformamide system was extracted with ethyl acetate (30mL×3), the organic phases were combined, dried over anhydrous magnesium sulfate, Suction filtration, the crude product after removing the solvent under reduced pressure, and then using the mixed solution of petroleum ether and ethyl acetate (V _{petroleum ether} : V _{ethyl acetate} = 10: 1) as eluent, can obtain benzene-containing Pure ring and chlorine substituted triazole compounds.

In the above preparation method, the first compound represented by the general formula II can be obtained by reacting the intermediate represented by the general formula IV with sodium azide in dimethyl sulfoxide (DMSO), and the specific operation can refer to the literature (Organic Letters, 2009 , 11(23):5490-5493) synthetic method. The preparation method of the first compound represented by general formula II is as follows:

In the above reaction, R represents H, a halogen atom, methoxy, ethoxy, benzyloxy, nitro or dimethylamino.

The preparation of the intermediate represented by the general formula IV: take benzaldehyde or substituted benzaldehyde and nitromethane as raw materials, in methanol as a solvent, dropwise add NaOH solution with a mass fraction of 20% at 0°C, and then The reaction can give intermediate Ⅳ. The specific operation can refer to the synthesis method in the literature (Tetrahedron Letters, 2012, 53(24): 2980-2984). The chemical reaction formula for preparing intermediate IV is as follows:

In the above reaction, R represents H, a halogen atom, methoxy, ethoxy, benzyloxy, nitro or dimethylamino.

At the same time, the present invention also provides a fungicide, which contains the above-mentioned triazole compound containing a benzene ring and a halogen substitution. The above-mentioned triazole compound containing benzene ring and halogen substitution has good bactericidal activity on crop pathogens, and can be used as a fungicide for pathogens produced during the growth of crops.

When the compound of the present invention is used as a fungicide, the compound of the present invention can be mixed with other plant protection-approved carriers or diluents, thereby making various dosage forms commonly used, such as powder, wettable powder, granule, Suspension agent, water emulsion, etc., can also be used in combination with other fungicides or at the same time.

The present invention also provides a use of the above-mentioned triazole compound containing a benzene ring and a halogen substitution or the above-mentioned sterilizing composition for inhibiting and killing pathogens during the growth of crops. The germs referred to therein include but are not limited to Fusarium rubella wheat, Phytophthora capsici, Alternaria rubella tobacco, Botrytis cinerea, Rice sheath blight or Sclerotinia sclerotiorum. In a preferred embodiment of the present invention, the general screening concentration of the above-mentioned triazole compound containing benzene ring and halogen substitution is 25 mg/L.

In the above-mentioned phenyl ring-containing and halogen-substituted triazole compound or the above-mentioned plant fungicide composition provided by the present invention inhibits or kills the pathogens produced during the growth of crops, different compounds can kill different pathogens Effects vary. Targeted selection of appropriate compounds is conducive to improving the killing effect of germs. In a preferred embodiment of the present invention, the preferred compounds corresponding to different bacteria are as follows:

When the pathogen is Gibberella tritici, the above-mentioned triazole compound containing a benzene ring and a halogen substitution is preferably that the 4-position of the triazole ring in formula I is a chlorine atom, and the benzene ring contains a hydrogen, chlorine atom or nitro substituent. The structure of the more preferred triazole compound containing benzene ring and halogen substitution is:

When the pathogen is Phytophthora capsici, the above-mentioned triazole compound is preferably that the 4-position of the triazole ring in formula I is a chlorine atom or a bromine atom, and the benzene ring contains a hydrogen, chlorine atom or nitro substituent. The more preferred structure of the above-mentioned triazole compound containing benzene ring and halogen substitution is:

When the pathogen is Alternaria tabacum, the above-mentioned triazole compound is preferably that the 4-position of the triazole ring in formula I is a chlorine atom, and the benzene ring contains a hydrogen or nitro substituent. The more preferred structure of the above-mentioned triazole compound containing benzene ring and halogen substitution is:

When the pathogen is Botrytis cinerea, the above-mentioned triazole compound is preferably that the 4-position of the triazole ring in formula I is a chlorine atom or a bromine atom, and the benzene ring contains hydrogen, chlorine atom, bromine atom, fluorine atom or nitro substituent . The more preferred structure of the above-mentioned triazole compound containing benzene ring and halogen substitution is:

When the pathogen is rice sheath blight, the above-mentioned triazole compound is preferably that the 4-position of the triazole ring in formula I is a chlorine atom, and the benzene ring contains a hydrogen atom. The more preferred structure of the above-mentioned triazole compound containing benzene ring and halogen substitution is:

When the pathogen is Sclerotinia sclerotiorum, the above-mentioned triazole compound is preferably that the 4-position of the triazole ring in formula I is chlorine atom or bromine atom, and the benzene ring contains hydrogen, chlorine atom, bromine atom or nitro substituent. The structure of the more preferred triazole compound containing benzene ring and halogen substitution is:

The synthesis methods and beneficial effects of triazole compounds 1 to 17 containing benzene ring and halogen substitution will be described below in conjunction with specific examples.

The preparation method of the compound of the present invention is specifically illustrated by implementing examples below.

Example 1

Preparation of Ⅰ-1:

Add 0.3 g (1.67 mmol) of 4-(2-chlorophenyl)-2H-1,2,3-triazole and 0.45 g (2.5 mmol) of NBS into a 50 mL single-port reaction flask, add 10 mL of isopropyl acetate, Reflux reaction, TLC monitoring reaction progress. After reacting for 5 hours, the solvent was removed under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography using a mixed solution of petroleum ether and ethyl acetate (V _{petroleum ether} : V _{ethyl acetate} = 10:1) to obtain a white solid 0.47 g, melting point: 78-80°C, yield 84%.

Elemental analysis: calculated value C% 37.17, H% 1.95, N% 16.26; found value C% 37.08, H% 1.92, N% 16.28.

The detection data of the obtained white solid is ¹ H NMR (400MHz, CDCl ₃ ) (δ/ppm): 7.35-7.54 (m, 4H, PhH), 12.63 (s, 1H, NH); EI MS: m/z (%)259([M+1] ⁺ ,38),258(M+,3),257([M-1] ⁺ ,29),152(14),150(100),123(32),130 (100), 114(21), 75(12). From the above analysis data, it can be seen that the compound prepared by this method is 4-bromo-5-(2-chlorophenyl)-2H-1,2,3-triazole. It is a kind of triazole compound containing benzene ring and halogen substitution represented by general formula I in the present invention.

Example 2

Preparation of Ⅰ-2:

Add 0.2g (0.83mmol) of 4-(2-bromo-4-fluorophenyl)-2H-1,2,3-triazole and 0.22g (1.24mmol) of NBS into a 50mL single-port reaction flask, add isoacetic acid Propyl ester 10mL, reflux reaction, TLC monitors the reaction progress. After reacting for 5 hours, the solvent was removed under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography using a mixed solution of petroleum ether and ethyl acetate (V _{petroleum ether} : V _{ethyl acetate} = 10:1) to obtain a colorless oil Compound 0.24g, yield 96%.

Elemental analysis: calculated value C% 29.94, H% 1.26, N% 13.09; found value C% 29.88, H% 1.22, N% 13.03.

The detection data of the obtained colorless oil is ¹ H NMR (400MHz, CDCl ₃ ) (δ/ppm): 7.13-7.48 (m, 3H, PhH), 12.49 (s, 1H, NH); EI MS: m ^{/z(%)322.9([M+2]+,7),320.9(M+,15),318.9([M-1]+,8),213.9(97),211.9(100),161(6 )} ,133(36),106(18). From the above analysis data, it can be seen that the compound prepared by this method is 4-bromo-5-(2-bromo-4-fluorophenyl)-2H-1,2,3-triazole. It is a kind of triazole compound containing benzene ring and halogen substitution represented by general formula I in the present invention.

Example 3

Preparation of Ⅰ-5:

Add 0.3g (1.34mmol) of 4-(2-bromophenyl)-2H-1,2,3-triazole and 0.35g (2.0mmol) of NBS into a 50mL single-port reaction flask, add 10mL of isopropyl acetate, and reflux The reaction was monitored by TLC. After reacting for 6 hours, the solvent was removed under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography using a mixed solution of petroleum ether and ethyl acetate (V _{petroleum ether} : V _{ethyl acetate} = 10:1) to obtain a white solid 0.38 g, melting point: 80-81°C, yield 95%.

Elemental analysis: calculated value C% 31.72, H% 1.66, N% 13.87; measured value C% 31.67, H% 1.59, N% 13.83.

The detection data of the obtained white solid is ¹ H NMR (400MHz, CDCl ₃ ) (δ/ppm): 7.26-7.72 (m, 4H, PhH), 13.21 (s, 1H, NH); EI MS: m/z (%)304.9([M+2] ⁺ ,23),302.9(M+,47),318.9([M-2] ⁺ ,23),224(9),207(8),197(20),196 (100), 194(98), 143(26), 116(71), 88(41). It can be seen from the above analysis data that the compound prepared by this method is 4-bromo-5-(2-bromophenyl)-2H-1,2,3-triazole. It is a kind of triazole compound containing benzene ring and halogen substitution represented by general formula I in the present invention.

Example 4

Preparation of Ⅰ-11:

Add 4-(3-nitrophenyl)-2H-1,2,3-triazole 0.3g (1.58mmol) and NCS0.27g (2.01mmol) into a 50mL single-port reaction flask, add N,N-dimethyl 8 mL of methyl formamide, the temperature was raised to 50° C., and the reaction progress was monitored by TLC. After reacting for 12 hours, the system was cooled to room temperature and then transferred to 100 mL of water, extracted with ethyl acetate (30 mL×3), the organic phases were combined, dried over anhydrous magnesium sulfate, filtered with suction, and the solvent was removed under reduced pressure to obtain a crude product. Using a mixed solution of petroleum ether and ethyl acetate (V _{petroleum ether} : V _{ethyl acetate} = 10:1) as the eluent, purified by silica gel column chromatography to obtain 0.19 g of a white solid, melting point: 161-162 ° C, yield 54%.

Elemental analysis: calculated value C% 42.78, H% 2.24, N% 24.94; found value C% 42.71, H% 2.22, N% 24.98.

The detection data of the obtained white solid is ¹ H NMR (400MHz, CDCl ₃ ) (δ/ppm): 7.26-8.86 (m, 4H, PhH), 11.76 (s, 1H, NH); EI MS: m/z (%)225([M+1] ⁺ ,10),224(M+,100),180(13),178(42),166(16),123(40),114(16),88(11 ),75(10). From the above analysis data, it can be seen that the compound prepared by this method is 4-chloro-5-(3-nitrophenyl)-2H-1,2,3-triazole. It is a kind of triazole compound containing benzene ring and halogen substitution represented by general formula I in the present invention.

Example 5

Preparation of Ⅰ-13:

Add 0.3g (2.1mmol) of 4-phenyl-2H-1,2,3-triazole and 0.36g (2.7mmol) of NCS into a 50mL single-port reaction flask, add 8mL of N,N-dimethylformamide, The temperature was raised to 50°C, and the progress of the reaction was monitored by TLC. After reacting for 10 h, the system was cooled to room temperature and then transferred to 100 mL of water, extracted with ethyl acetate (30 mL×3), the organic phases were combined, dried over anhydrous magnesium sulfate, filtered with suction, and the solvent was removed under reduced pressure to obtain a crude product. Using a mixed solution of petroleum ether and ethyl acetate (V _{petroleum ether} : V _{ethyl acetate} = 10:1) as the eluent, purified by silica gel column chromatography to obtain 0.21 g of a white solid, melting point: 137-138 °C, yield 58%.

Elemental analysis: calculated value C% 53.50, H% 3.37, N% 23.40; measured value C% 53.42, H% 3.28, N% 23.46.

The detection data of the obtained white solid is ¹ H NMR (400MHz, CDCl ₃ ) (δ/ppm): 7.26-7.93 (m, 5H, PhH), 11.72 (s, 1H, NH); EI MS: m/z (%) 180([M+1] ⁺ ,10),179(M+,100),150(7),124(22),116(20),89(45),76(11). From the above analysis data, it can be seen that the compound prepared by this method is 4-chloro-5-phenyl-2H-1,2,3-triazole. It is a kind of triazole compound containing benzene ring and halogen substitution represented by general formula I in the present invention.

Example 6

Preparation of Ⅰ-16:

Add 4-(3,4-dimethoxyphenyl)-2H-1,2,3-triazole 0.2g (0.97mmol) and NCS 0.17g (1.27mmol) in a 50mL single-port reaction flask, add N , N-dimethylformamide 8mL, the temperature was raised to 50°C, and the reaction progress was monitored by TLC. After reacting for 12 hours, the system was cooled to room temperature and then transferred to 100 mL of water, extracted with ethyl acetate (30 mL×3), the organic phases were combined, dried over anhydrous magnesium sulfate, filtered with suction, and the solvent was removed under reduced pressure to obtain a crude product. Using a mixed solution of petroleum ether and ethyl acetate (V _{petroleum ether} : V _{ethyl acetate} = 10:1) as the eluent, purified by silica gel column chromatography to obtain 0.19 g of a light yellow solid, melting point: 218-220°C, collected The rate is 83%.

Elemental analysis: calculated value C% 50.12, H% 4.21, N% 17.53; found value C% 50.08, H% 4.16, N% 17.49.

The detection data of the obtained light yellow solid is ¹ HNMR (400MHz, CDCl ₃ ) (δ/ppm): 3.92 (s, 6H, 2×CH ₃ ), 6.92-7.55 (m, 3H, PhH), 11.87 (s , 1H, NH); EI MS: m/z (%) 240 ([M+1] ⁺ , 12), 239 (M+, 100), 224 (28), 133 (10). It can be seen from the above analysis data that the compound prepared by this method is 4-chloro-5-(3,4-dimethoxyphenyl)-2H-1,2,3-triazole. It is a kind of triazole compound containing benzene ring and halogen substitution represented by general formula I in the present invention.

Other triazole compounds containing a benzene ring and a halogen substitution represented by the general formula I of the present invention can be prepared by using a preparation method similar to that of the above-mentioned Examples 1 to 6. The other 11 compounds can be prepared by the preparation method in Example 1 or 4, and the structures, ¹ H NMR data, The physical properties and yields are listed in Table 1.

Table 1 Structure, ¹ H NMR data, physical properties and yield of triazole compounds containing benzene ring and halogen substitution

test:

Bactericidal activity test (stereoactivity method)

Bacteria tested: Gibberella zeae, Phytophythoracapsici, Alternaria alternata, Botrytis cinerea, Rhizoctonia solani and Sclerotia sclerotiorum Bacteria (Sclerotonia sclerotiorum).

The test method adopts the drug-containing medium method to carry out the bactericidal activity test, and the specific steps are as follows:

Take 0.05g of each compound in the above I-1 to I-17, dissolve it in 0.20mL of DMF, add 98.8mL of sterile water containing 0.1% Tween80 emulsifier, stir well, and prepare a solution with a concentration of 500mg/L. Take 2 mL of each 500 mg/L compound solution and add it to 38 mL of potato agar medium (PDA) cooled to 45°C to prepare a drug-containing medium plate with a final concentration of 25 mg/L. Take the 6.0mm diameter mycelial block from the edge of the cultured test bacteria colony, and move it to the drug-containing medium. After the treatment, they were cultured in a constant temperature biochemical incubator at 28°C. A blank control was set in the experiment. After 4 days, the colony diameter was measured and the growth inhibition rate was calculated.

Measuring results: The classification standard of activity level is expressed as "+++" between 80% and 100%, "++" between 60% and 79%, and "+" between 40% and 59%. , with "-" below 40%, the specific test results are shown in Table 2.

Table 2 The general screening test results of bactericidal activity of triazole compounds containing benzene ring and halogen substitution

It can be seen from Table 2 that compounds Ⅰ-10, Ⅰ-11 and Ⅰ-13 have good inhibitory effects on crop pathogens such as wheat head blight, capsicum phytophthora, tobacco red star, cucumber gray mold and rape sclerotinia Effect. Referring to the above test method, further by reducing the concentration of the three compounds (respectively 10mg/L, 5mg/L, 2.5mg/L), and using the commercial variety difenoconazole as a control, the three compounds were investigated. Inhibitory activity against crop pathogens at low application rates. Table 3 shows the results of the preliminary screening test for the fungicidal activity of the three compounds Ⅰ-10, Ⅰ-11 and Ⅰ-13.

Table 3 Results of the preliminary screening test for the bactericidal activity of compounds Ⅰ-10, Ⅰ-11 and Ⅰ-13

It can be seen from Table 3 that the inhibitory activity of compounds Ⅰ-10, Ⅰ-11 and Ⅰ-13 on wheat scab, capsicum phytophthora, tobacco Alternaria and cucumber Botrytis cinerea decreases with the decrease of dosage concentration, However, the three compounds have excellent antibacterial effects on Sclerotinia sclerotiorum at the dosage concentration of 10 mg/L, especially compound Ⅰ-13 has excellent antibacterial effect on Sclerotinia sclerotiorum at 5 mg/L and 2.5 mg/L. Still showed excellent antibacterial effect.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes, and within the spirit and principles of the present invention, any modifications, equivalent replacements, improvements, etc., should be included in the protection scope of the present invention within.

Claims (9)

1. a class contains phenyl ring and the substituted triazole compounds of halogen, it is characterised in that described containing phenyl ring and halogen substituted triazole chemical combination Thing have below formula I represent structure:

In formula I, R is hydrogen, halogen atom, methoxyl group, ethyoxyl, benzyloxy, nitro or dimethylamino；

X is bromine atoms or chlorine atom.

The most according to claim 1 containing the substituted triazole compounds of phenyl ring and halogen, it is characterised in that selected from following chemical combination Thing:

3. the preparation method containing the substituted triazole compounds of phenyl ring and halogen described in any one of claim 1-2, its feature It is, by being contained described in acquisition with being reacted by the second compound represented by general formula III by the first compound represented by formula II Phenyl ring and the substituted triazole compounds of halogen, described formula II and described general formula III are as follows:

In described II, R is hydrogen, halogen atom, methoxyl group, ethyoxyl, benzyloxy, nitro or dimethylamino；

In described III, X is bromine atoms or chlorine atom.

Preparation method the most according to claim 3, it is characterised in that:

When described second compound is N-bromosuccinimide, concrete preparation method is: with isopropyl acetate as solvent, It is 1 1.2～1.5 with described N-bromosuccinimide by the ratio of the amount of material by described first compound, under counterflow condition, React 5～12 hours, obtain containing the substituted triazole compounds of phenyl ring and bromine；

When described second compound is N-chlorosuccinimide, concrete preparation method is: with DMF For solvent, it is 1 1.2～1.5 with described N-chlorosuccinimide by the ratio of the amount of material by described first compound, reaction Temperature is 45～50 DEG C, reacts 5～12 hours, obtains containing the substituted triazole compounds of phenyl ring and chlorine.

5. according to the preparation method described in claim 3 or 4, it is characterised in that:

When described second compound is N-bromosuccinimide, concrete preparation method is: with isopropyl acetate as solvent, It is 1 1.5 with described N-bromosuccinimide by the ratio of the amount of material by described first compound, under counterflow condition, reacts 5 ～12 hours, obtain containing the substituted triazole compounds of phenyl ring and bromine；

When described second compound is N-chlorosuccinimide, concrete preparation method is: with DMF For solvent, being 1 1.5 with described N-chlorosuccinimide by the ratio of the amount of material by described first compound, reaction temperature is 45～50 DEG C, react 5～12 hours, obtain containing the substituted triazole compounds of phenyl ring and chlorine.

6. a series bactericidal agent, it is characterised in that the main active of described antibacterial comprises institute any one of claim 1-2 State containing the substituted triazole compounds of phenyl ring and halogen.

7. containing described in phenyl ring and the substituted triazole compounds of halogen or claim 6 described in a class any one of claim 1-2 Antibacterial has suppression and the purposes of killing effect to the pathogenic bacteria produced in process of crop growth.

Purposes the most according to claim 7, it is characterised in that described pathogenic bacteria be fusarium graminearum, P. capsici, Tobacco brown spot pathogen, botrytis cinerea pers, Rhizoctonia solani Kuhn or Sclerotinia sclerotiorum.

9. according to the purposes described in any one of claim 7-8, it is characterised in that:

When described pathogenic bacteria is fusarium graminearum, the described structure containing the substituted triazole compounds of phenyl ring and halogen is as follows:

When described pathogenic bacteria is P. capsici, the described structure containing the substituted triazole compounds of phenyl ring and halogen is as follows:

When described pathogenic bacteria is tobacco brown spot pathogen, the described structure containing the substituted triazole compounds of phenyl ring and halogen is as follows:

When described pathogenic bacteria is botrytis cinerea pers, the described structure containing the substituted triazole compounds of phenyl ring and halogen is as follows:

When described pathogenic bacteria is Rhizoctonia solani Kuhn, the described structure containing the substituted triazole compounds of phenyl ring and halogen is as follows:

When described pathogenic bacteria is Sclerotinia sclerotiorum, the described structure containing the substituted triazole compounds of phenyl ring and halogen is as follows: