CN111377869A - Halogenated phenylhydrazone compound of dihalogenated pyrazole formaldehyde, preparation method and application thereof - Google Patents
Halogenated phenylhydrazone compound of dihalogenated pyrazole formaldehyde, preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of bactericides and discloses a halogenated phenylhydrazone compound of dihalogenated pyrazole formaldehyde, a preparation method and application thereof, wherein the structure of the compound is shown as the formula (I):
Description
Technical Field
The invention relates to a halogenated phenylhydrazone compound of dihalogenated pyrazole formaldehyde, a preparation method and application thereof in preventing and treating plant fungal diseases, and has application in preparing pesticide bactericides.
Background
The halopyrazole is an active substructure and has wide application in the fields of bactericide creation and plant fungal disease control, such as amide compounds containing chloropyrazole (organic chemistry, 2003, (10): 1131-. Furazolid (furametpyr) and penflufen (penflufen) serving as bactericides respectively contain chloropyrazole and fluoropyrazole, and can effectively prevent and treat plant fungal diseases.
Hydrazone is also an important structural unit in the bactericide structure, and the molecular structures of the bactericides such as quinoxalin hydrazone (halogenated) and pyriizone (ferimzone) respectively contain benzoyl hydrazone and pyrimidine hydrazone groups. Hydrazone is also often introduced when designing the molecular structure of novel fungicides, and compounds such as halophenylhydrazone (Organic & Biomolecular Chemistry, 2015, 13 (2): 477-486.), acetylhydrazone (CN 1331080, 2002-01-16) and formylhydrazone (Proc. Natl. Acad. Med. 2004, (03): 67-70.) all show good activity of inhibiting plant pathogenic fungi.
According to the invention, dihalogenated pyrazole and halogenated phenylhydrazone are introduced into the same molecular structure according to the splicing principle of an active substructure, a series of halogenated phenylhydrazone compounds of dihalogenated pyrazole formaldehyde with novel structures are designed and synthesized, and biological activity determination shows that the compounds have obvious inhibitory activity on plant pathogenic fungi.
Disclosure of Invention
The invention aims to provide a halogenated phenylhydrazone compound of dihalogenated pyrazole formaldehyde.
The second purpose of the invention is to provide a preparation method of a halogenated benzene hydrazone compound of dihalogenated pyrazole formaldehyde.
The third purpose of the invention is to provide the application of the compound.
The invention provides a halogenated benzene hydrazone compound of dihalogen pyrazole formaldehyde with a structure shown in a general formula (I),
in formula (I), the various groups have the definitions set forth below:
X1、X2each selected from a halogen atom;
Y(n)wherein n is a 1-5 substitution, Y(n)Selected from 1-5 halogen atoms;
r is selected from hydrogen and C1-6An alkyl group.
In formula (I), the respective groups have the preferred definitions as described below:
X1＝X2selected from F, Cl, Br;
Y(n)wherein n is a 1-2 substitution, Y(n)Selected from 1-2 halogen atoms selected from F, Cl, Br;
r is selected from hydrogen and C1-3An alkyl group.
In formula (I), the respective groups have further preferred definitions as described below:
X1＝X2selected from Cl;
Y(n)selected from 2-F, 4-F, 2-Cl, 3-Cl, 4-Br, 2, 4-Cl2；
R is selected from hydrogen and methyl.
In a second aspect of the present invention, there is provided a method for preparing a dihalopyrazolecarboxaldehyde halogenophenylhydrazone compound of formula (I), which comprises reacting a compound of formula (II) with a substituted phenylhydrazine of formula (III) to prepare a dihalopyrazolecarboxaldehyde halogenophenylhydrazone compound of formula (I), wherein the reaction equation is represented by the following general formula (A):
wherein in each of the above structural formulae:
X1、X2、Y(n)and R have the definitions of the corresponding groups as described above.
The third aspect of the invention relates to application of a dihalogenated pyrazolecarboxaldehyde halogeno-benzene hydrazone compound shown in the formula (I) in the aspects of inhibiting plant pathogenic fungi and preventing and treating plant fungal diseases, and the dihalogenated pyrazolecarboxaldehyde halogeno-benzene hydrazone compound can be used as a bactericide and applied to the field of pesticides.
The compound is suitable for inhibiting wheat scab, strawberry botrytis cinerea and rice sheath blight germ.
The compound is suitable for preventing and treating wheat scab, strawberry gray mold and rice sheath blight.
Has the advantages that:
1. the invention discloses a dihalogenated pyrazole formaldehyde halogenated phenylhydrazone compound with a novel molecular structure shown in a formula (I), wherein the structural formula contains a dihalogenated pyrazole group and a halogenated phenylhydrazone group, and the dihalogenated pyrazole formaldehyde halogenated phenylhydrazone compound is characterized in that pyrazole is linked with the hydrazone group through methine on a C atom at the 4-position of the pyrazole.
2. The preparation method of the dihalogenated benzene hydrazone compound of the dihalogenated pyrazole formaldehyde disclosed by the invention is simple and convenient, and has the advantages of easily obtained raw materials and high yield.
3. The halogenated phenylhydrazone compound of the dihalogenated pyrazole formaldehyde disclosed by the invention has obvious activity of inhibiting plant pathogenic fungi, can be applied to control plant diseases caused by the pathogenic fungi, and has application as a pesticide bactericide.
Detailed Description
The essential features of the invention can be seen from the following examples, which should not be construed as limiting the invention in any way.
Preparation examples
Example 1: preparation of dihalo-pyrazolecarboxaldehyde halogeno-phenylhydrazone compound I-a of the present invention
Adding 15mL of ethanol, a compound II-a (3mmol) and 2-chlorophenylhydrazine III-a (3mmol) into a 50mL single-neck flask, taking 1 drop of acetic acid as a catalyst, heating and refluxing for 2 hours, separating out a solid, cooling, performing suction filtration, washing a filter cake twice by using a small amount of glacial ethanol, and drying to obtain a yellow powdery solid I-a, wherein the reaction equation is as follows:
using the method of example 1, I-a to I-n compounds among halogenophenylhydrazone compounds (I) of dihalopyrazolecarboxaldehyde were prepared:
3, 5-dichloro-4- ((2- (2-chlorophenyl) hydrazone group) methyl) -1H-pyrazole (I-a)
A yellow powder; the yield is 61.17%; m.p.225.1-227.8 ℃; IR (KBr, cm)-1)v：3310，3107，2879，1597，1517，1457，1291，1139，988，737，711；1H NMR(400MHz，DMSO-d6)δ：14.11(s，1H)，10.02(s，1H)，8.19(s，1H)，7.49(d，J＝8.2Hz，1H)，7.32(d，J＝7.9Hz，1H)，7.25(t，J＝7.7Hz，1H)，6.78(t，J＝7.6Hz，1H)；13C NMR(100MHz，DMSO-d6)δ：141.83，130.46，129.79，128.52，119.97，116.38，114.20，111.01；HR-MS(ESI)：m/z calcd for C10H7Cl3N4([M+H]+)288.9809，found 288.9810.
3, 5-dichloro-4- ((2- (3-chlorophenyl) hydrazone group) methyl) -1H-pyrazole (I-b)
A yellow powder; the yield is 65.02%; m.p.164.5-167.2 ℃; IR (KBr, cm)-1)v：3321，3127，2921，1596，1520，1388，1244，1131，990，763，677；1H NMR(400MHz，DMSO-d6)δ：12.49(s，1H)，10.07(s，1H)，7.71(s，1H)，7.17(t，J＝8.0Hz，1H)，7.03(s，1H)，6.85(d，J＝8.2Hz，1H)，6.69(d，J＝7.8，1.2Hz，1H)；13C NMR(100MHz，DMSO-d6)δ：147.05，134.30，131.21，127.78，118.58，111.53，110.93，110.84；HR-MS(ESI)：m/z calcd for C10H7Cl3N4([M+H]+)288.9809，found 288.9807.
3, 5-dichloro-4- ((2- (4-chlorophenyl) hydrazone group) methyl) -1H-pyrazole (I-c)
A grayish green powder; the yield is 64.80%; m.p.134.1-135.4 deg.C; IR (KBr, cm)-1)v：3303，3131，2911，1597，1516，1479，1253，1132，991，797，634；1H NMR(400MHz，DMSO-d6)δ：14.11(s，1H)，10.48(s，1H)，7.70(s，1H)，7.24(dd，J＝8.7，2.4Hz，2H)，7.04-6.96(m，2H)；13C NMR(100MHz，DMSO-d6)δ：144.55，129.39，127.13，122.42，113.63，110.97；HR-MS(ESI)：m/zcalcd for C10H7Cl3N4([M+H]+)288.9809，found 288.9807.
3, 5-dichloro-4- ((2- (2, 4-dichlorophenyl) hydrazone) methyl) -1H-pyrazole (I-d)
A white powder; the yield is 72.24%; m.p.237.3-238.8 ℃; IR (KBr, cm)-1)v：3312，3128，2913，1594，1495，1374，1284，1121，981，737，640；1H NMR(400MHz，DMSO-d6)δ：14.18(s，1H)，10.14(s，1H)，8.21(s，1H)，7.49-7.43(m，2H)，7.31(d，J＝8.9Hz，1H)；13C NMR(100MHz，DMSO-d6)δ：141.02，131.23，128.98，128.51，122.53，116.83，115.12，110.86；HR-MS(ESI)：m/z calcd for C10H6Cl4N4([M+H]+)324.9390，found 324.9383.
3, 5-dichloro-4- ((2- (2-fluorophenyl) hydrazone group) methyl) -1H-pyrazole (I-e)
A brown powder; the yield is 60.11%; m.p.202.5-204.1 deg.C; IR (KBr, cm)-1)v：3315，3107，2917，1625，1548，1469，1387，1255，1127，990，896，741；1H NMR(400MHz，DMSO-d6)δ：14.13(s，1H)，10.28(s，1H)，8.01(s，1H)，7.45(dd，J＝12.0，4.6Hz，1H)，7.17-7.04(m，2H)，6.74(ddd，J＝9.0，7.6，1.4Hz，1H)；13C NMR(100MHz，DMSO-d6)δ：150.53，148.16，133.81(d，J＝9.7Hz)，129.29，125.45(d，J＝3.0Hz)，118.95(d，J＝6.6Hz)，115.44(d，J＝17.5Hz)，114.03(d，J＝3.3Hz)，111.02；HR-MS(ESI)：m/z calcd for C10H7Cl2FN4([M+H]+)273.0105，found 273.0094.
3, 5-dichloro-4- ((2- (4-fluorophenyl) hydrazone group) methyl) -1H-pyrazole (I-f)
A yellow powder; the yield is 65.37%; m.p.102.3-103.9 deg.C; IR (KBr, cm)-1)v：3307，3123，2968，1508，1389，1216，1133，992，817，772，658；1H NMR(400MHz，DMSO-d6)δ：14.09(s，1H)，10.36(s，1H)，7.67(s，1H)，7.06(t，J＝8.8Hz，2H)，6.99(dd，J＝9.0，4.8Hz，2H)；13C NMR(100MHz，DMSO-d6)δ：157.47，155.15，142.34，126.27，116.21，115.99，113.15，113.08，111.11；HR-MS(ESI)：m/z calcd for C10H7Cl2FN4([M+H]+)273.0105.found 273.0094.
3, 5-dichloro-4- ((2- (4-bromophenyl) hydrazone group) methyl) -1H-pyrazole (I-g)
A yellow powder; the yield is 63.19%; m.p.168.8-170.4 ℃; IR (KBr, cm)-1)v：3307，3131，2969，1507，1388，1216，1132，991，816，772，657；1H NMR(400MHz，DMSO-d6)δ：14.13(s，1H)，10.52(s，1H)，7.70(s，1H)，7.36(d，J＝8.6Hz，2H)，6.95(d，J＝8.6Hz，2H)；13C NMR(100MHz，DMSO-d6)δ：144.92，132.21，127.24，114.15，110.96，109.98；HR-MS(ESI)：m/z calcd forC10H7Cl2BrN4([M+H]+)334.9280，found 334.9279.
3, 5-dichloro-4- ((2- (2-chlorophenyl) hydrazone group) methyl) -1-methyl-1H-pyrazole (I-H)
A yellow powder; the yield is 71.19%; m.p.123.5-124.7 ℃; IR (KBr, cm)-1)v：3237，2984，2896，1591，1537，1458，1295，1244，1030，897，740；1H NMR(400MHz，DMSO-d6)δ：10.03(s，1H)，8.18(s，1H)，7.49(d，J＝8.2Hz，1H)，7.32(d，J＝7.9Hz，1H)，7.25(t，J＝7.7Hz，1H)，6.79(t，J＝7.6Hz，1H)，3.82(s，3H)；13C NMR(100MHz，DMSO-d6)δ：141.81，136.26，130.31，129.74，128.47，126.38，119.93，116.42，114.22，111.86，37.05；HR-MS(ESI)：m/z calcdfor C11H9Cl3N4([M+H]+)302.9966，found 302.9961.
3, 5-dichloro-4- ((2- (3-chlorophenyl) hydrazone group) methyl) -1-methyl-1H-pyrazole (I-I)
A yellow powder; the yield is 67.06%; m.p.151.9-153.6 deg.C; IR (KBr, cm)-1)v：3257，2988，2896，1592，1543，1392，1241，1084，927，849，780，686；1H NMR(400MHz，DMSO-d6)δ：10.59(s，1H)，7.69(s，1H)，7.22(t，J＝8.0Hz，1H)，7.01(s，1H)，6.92(d，J＝8.2Hz，1H)，6.76(dd，J＝7.8，1.2Hz，1H)，3.81(s，3H)；13C NMR(100MHz，DMSO-d6)δ：147.02，136.02，134.30，131.19，127.64，126.15，118.61，111.68，111.57，110.94，37.07；HR-MS(ESI)：m/z calcd forC11H9Cl3N4([M+H]+)302.9966，found 302.9961.
3, 5-dichloro-4- ((2- (4-chlorophenyl) hydrazone) methyl) -1-methyl-1H-pyrazole (I-j)
A yellow powder; the yield is 65.20%; m.p.159.6-161.8 ℃; IR (KBr, cm)-1)v：3232，2988，2896，1595，1538，1408，1130，1097，826，781；1H NMR(400MHz，DMSO-d6)δ：10.51(s，1H)，7.68(s，1H)，7.25(d，J＝8.7Hz，2H)，7.00(d，J＝8.7Hz，2H)，3.82(d，J＝9.9Hz，3H)；13C NMR(100MHz，DMSO-d6)δ：144.51，135.96，129.37，126.98，125.98，122.47，113.63，111.80，37.05；HR-MS(ESI)：m/z calcd for C11H9Cl3N4([M+H]+)302.9966，found 302.9959.
3, 5-dichloro-4- ((2- (2, 4-dichlorophenyl) hydrazone) methyl) -1-methyl-1H-pyrazole (I-k)
A yellow powder; the yield is 72.62%; m.p.170.2-172.1 ℃; IR (KBr, cm)-1)v：3311，2967，2901，1594，1502，1388，1283，1127，1048，807，770；1H NMR(400MHz，DMSO-d6)δ：10.16(s，1H)，8.19(s，1H)，7.49-7.41(m，2H)，7.31(dd，J＝8.9，2.0Hz，1H)，3.82(s，3H)；13C NMR(100MHz，DMSO-d6)δ：140.97，136.30，131.11，129.00，128.55，126.63，122.57，116.84，115.14，111.66，37.13；HR-MS(ESI)：m/z calcd for C11H8Cl4N4([M+H]+)338.9547，found338.9546.
3, 5-dichloro-4- ((2- (2-fluorophenyl) hydrazone group) methyl) -1-methyl-1H-pyrazole (I-l)
A yellow powder; the yield is 61.58%; m.p.123.3-124.6 ℃; IR (KBr, cm)-1)v：3261，2984，2896，1627，1543，1391，1255，1125，1081，906，749；1H NMR(400MHz，DMSO-d6)δ：10.31(s，1H)，7.98(s，1H)，7.44(t，J＝7.7Hz，1H)，7.17-7.06(m，2H)，6.76(ddd，J＝9.2，6.3，1.5Hz，1H)，3.81(s，3H)；13C NMR(100MHz，DMSO-d6)δ：149.40(d，J＝238.9Hz)，136.10，133.80(d，J＝9.7Hz)，129.21，126.21，125.44(d，J＝3.0Hz)，119.00(d，J＝6.7Hz)，115.42(d，J＝17.5Hz)，114.10，111.87，37.06；HR-MS(ESI)：m/z calcd for C11H9Cl2FN4([M+H]+)287.0261，found 287.0255.
3, 5-dichloro-4- ((2- (4-fluorophenyl) hydrazone) methyl) -1-methyl-1H-pyrazole (I-m)
A yellow powder; the yield is 67.23%; m.p.141.3-142.6 ℃; IR (KBr, cm)-1)v：3307，2984，2901，1627，1544，1499，1407，1258，1066，818，772；1H NMR(400MHz，DMSO-d6)δ：10.40(s，1H)，7.65(s，1H)，7.06(t，J＝8.9Hz，2H)，6.99(dd，J＝9.1，4.8Hz，2H)，3.81(s，3H)；13C NMR(100MHz，DMSO-d6)δ：156.32(d，J＝233.9Hz)，142.28，135.81，126.12，125.78，116.09(d，J＝22.4Hz)，113.13(d，J＝7.5Hz)，111.94，37.05；HR-MS(ESI)：m/z calcd for C11H9Cl2FN4([M+H]+)287.0261，found 287.0254.
3, 5-dichloro-4- ((2- (4-bromophenyl) hydrazone group) methyl) -1-methyl-1H-pyrazole (I-n)
A yellow powder; the yield is 69.96%; m.p.155.3-157.0 ℃; IR (KBr, cm)-1)v：3232，2988，2896，1590，1536，1483，1408，1254，1129，1129，889，775；1H NMR(400MHz，DMSO-d6)δ：10.53(s，1H)，7.68(s，1H)，7.36(d，J＝8.8Hz，2H)，6.95(d，J＝8.8Hz，2H)，3.82(d，J＝6.4Hz，3H)；13CNMR(100MHz，DMSO-d6)δ：144.87，135.97，132.20，127.10，126.02，114.16，111.79，110.03，37.07；HR-MS(ESI)：m/z calcd for C11H9Cl2BrN4([M+H]+)348.9437，found 348.9429.
Examples of the use
Example 2: the bactericidal activity of the halogenated phenylhydrazone compound (I) of dihalo-pyrazole formaldehyde is determined
The bactericidal activity of compounds I-a to I-n in the halophenylhydrazone compound (I) of dihalopyrazolecarboxaldehyde on 3 plant pathogenic bacteria of Fusarium graminearum, Botrytis cinerea and Rhizoctonia solani at the concentration of 10 mu g/mL is measured by adopting a hypha growth rate method.
The determination method comprises the following steps: dissolving 13.5mg of a test compound (including a control medicament carbendazim) in 1.5mL of DMSO, sucking 0.1mL of the solution, adding 0.1mL of the DMSO, mixing uniformly, sucking 0.1mL of the solution, adding into 44.9mL of sterilized potato dextrose agar medium (PDA medium), shaking uniformly to prepare a drug-containing medium with the concentration of 10 mu g/mL, and pouring into 3 sterile culture dishes with the diameter of 9 cm. The culture medium prepared by adding equal amount of solvent is used as blank control. Meanwhile, a culture medium with the concentration of 10 mug/mL prepared by adding the bactericide carbendazim is used as a medicament control. The bacterial colony which grows normally is punched by a puncher (with the inner diameter of 0.5cm) to prepare bacterial cake, the bacterial cake is inoculated into the center of the culture medium plate by an inoculating needle, and the bacterial cake is inversely cultured in an incubator at 25 ℃. The diameter of the colonies on the blank control medium was measured until the diameter reached 2/3 of the plate, and the diameter of each colony was measured 2 times by the cross method, and the average value (unit: cm) was calculated. Triplicates were set for each concentration treatment and for each of the three controls. And (3) calculating the growth inhibition rate after medicament treatment, wherein the calculation formula is as follows:
the calculation method comprises the steps of determining the inhibition ratio (%) - (diameter of solvent control colony-diameter of treated colony) ÷ (diameter of solvent control colony-0.5) × 100%
And (3) measuring results: the results of measuring the growth inhibition rate of the dihalopyrazolecarboxaldehyde halogenophenylhydrazone compound (I) against 3 test plant pathogenic bacteria are shown in Table 1.
TABLE 1 inhibition ratio (%, 10. mu.g/mL) of halophenylhydrazone compound (I) of dihalopyrazolecarboxaldehyde to 3 plant pathogenic bacteria
Table 1 shows that compounds I-a to I-n in halogenated phenylhydrazone compounds (I) of dihalogenated pyrazole formaldehyde have significant inhibitory activity against 3 test plant pathogenic bacteria of Gibberella tritici, Botrytis fragrans and Rhizoctonia solani at a concentration of 10 mu g/mL. The inhibition rate of each compound on the wheat scab germ is 42.26-71.92%, wherein the inhibition rate of the compounds I-b and I-m is more than 70%. The inhibition rate of each compound on the botrytis cinerea is 46.57-70.53%, wherein the inhibition rate of the compounds I-b and I-e is more than 70%. The inhibition rate of each compound on rice sheath blight bacteria is 54.04-70.87%, wherein the inhibition rate of the compounds I-f and I-n is more than 70%.
Claims (7)
1. A halogenated benzene hydrazone compound of dihalogenated pyrazole formaldehyde with a structure shown in a formula (I),
wherein the content of the first and second substances,
X1、X2each selected from a halogen atom;
Y(n)wherein n is a 1-5 substitution, Y(n)Selected from 1-5 halogen atoms;
r is selected from hydrogen and C1-6An alkyl group.
2. The dihalopyrazolecarboxaldehyde halophenylhydrazone compound according to claim 1, characterized in that:
X1＝X2selected from F, Cl, Br;
Y(n)wherein n is a 1-2 substitution, Y(n)Selected from 1-2 halogen atoms selected from F, Cl, Br;
r is selected from hydrogen and C1-3An alkyl group.
3. The dihalopyrazolecarboxaldehyde halophenylhydrazone compound according to claim 2, characterized in that:
X1＝X2selected from Cl;
Y(n)selected from 2-F, 4-F, 2-Cl, 3-Cl, 4-Br、2，4-Cl2；
R is selected from hydrogen and methyl.
4. A halophenylhydrazone compound of a dihalopyrazolecarboxaldehyde according to any one of claims 1 to 3, characterized by being prepared by a method represented by the general formula (A):
wherein in each of the above structural formulae:
X1、X2、Y(n)r both have the meanings as claimed in any of claims 1 to 3.
5. Use of a halophenylhydrazone compound of a dihalopyrazolecarboxaldehyde according to any one of claims 1 to 3 for controlling a fungal disease of a plant.
6. The use according to claim 5, characterized in that the halophenylhydrazones of dihalopyrazolecarboxaldehydes according to any one of claims 1 to 3 are used for inhibiting Gibberella tritici, Botrytis fragilis, Rhizoctonia solani.
7. The use according to claim 5, characterized in that the halogenated phenylhydrazones of dihalopyrazolecarboxaldehydes according to any of claims 1 to 3 are used for controlling wheat scab, strawberry gray mold and rice sheath blight.
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| CN114195707A (en) * | 2021-12-17 | 2022-03-18 | 西北农林科技大学 | High-efficiency broad-spectrum plant antibacterial agent BZ |
| CN116283822A (en) * | 2023-02-07 | 2023-06-23 | 西北农林科技大学 | Thiazole and imidazo [1,2-a ] pyridine acylhydrazone compounds and application thereof |
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| CN116283822A (en) * | 2023-02-07 | 2023-06-23 | 西北农林科技大学 | Thiazole and imidazo [1,2-a ] pyridine acylhydrazone compounds and application thereof |
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