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CN111377869A - A kind of halogenated phenylhydrazone compound of dihalogenated pyrazole carboxaldehyde, preparation method and application thereof - Google Patents

A kind of halogenated phenylhydrazone compound of dihalogenated pyrazole carboxaldehyde, preparation method and application thereof Download PDF

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CN111377869A
CN111377869A CN201811616786.4A CN201811616786A CN111377869A CN 111377869 A CN111377869 A CN 111377869A CN 201811616786 A CN201811616786 A CN 201811616786A CN 111377869 A CN111377869 A CN 111377869A
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杨春龙
焦健
陈敏
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Nanjing Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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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

一种二卤代吡唑甲醛的卤代苯腙类化合物、制备方法及其 应用A kind of halogenated phenylhydrazone compound of dihalogenated pyrazole carboxaldehyde, preparation method and same application

技术领域technical field

本发明涉及一种二卤代吡唑甲醛的卤代苯腙类化合物、制备方法及其在防治植物真菌病害方面的应用，具有制备农药杀菌剂的用途。The invention relates to a halogenated phenylhydrazone compound of dihalogenated pyrazole carboxaldehyde, a preparation method and its application in preventing and controlling plant fungal diseases, and has the application of preparing pesticide fungicides.

背景技术Background technique

卤代吡唑是一种活性亚结构，在杀菌剂创制和植物真菌病害防治领域具有广泛的应用，如含氯代吡唑的酰胺类化合物(有机化学，2003，(10)：1131-1134.)、含氯代吡唑的肟酯类化合物(应用化学，2005，(08)：829-834.)、含氯代吡唑的酰肼类化合物(农药学学报，2006，(04)：363-366.)、含溴代吡唑的酰胺类化合物(精细化工中间体，2007，(03)：27-29.)对植物病原真菌均具有杀菌活性。杀菌剂呋吡菌胺(furametpyr)和氟唑菌苯胺(penflufen)分别含有氯代吡唑和氟代吡唑，能够有效防治植物真菌病害。Halopyrazole is an active substructure, which has a wide range of applications in the field of fungicide creation and plant fungal disease control, such as amide compounds containing chloropyrazole (Organic Chemistry, 2003, (10): 1131-1134. ), oxime ester compounds containing chloropyrazole (Applied Chemistry, 2005, (08): 829-834.), hydrazide compounds containing chloropyrazole (Journal of Pesticide Science, 2006, (04): 363 -366.), amide compounds containing bromopyrazole (Fine Chemical Intermediates, 2007, (03): 27-29.) have bactericidal activity against phytopathogenic fungi. The fungicides furametpyr and penflufen contain chloropyrazole and fluoropyrazole, respectively, and can effectively control plant fungal diseases.

腙也是杀菌剂结构中的一种重要结构单元，如杀菌剂醌肟腙(benzoicacid)和嘧菌腙(ferimzone)的分子结构中分别含有苯甲酰腙和嘧啶腙基团。人们在设计新型杀菌剂的分子结构时也常常引入腙，如引入卤代苯腙(Organic&Biomolecular Chemistry，2015，13(2)：477-486.)、乙酰腙(CN 1331080，2002-01-16)、甲酰腙(农药学学报，2004，(03)：67-70.)的化合物均表现出良好的抑制植物病原真菌的活性。Hydrazone is also an important structural unit in the structure of fungicides. For example, the molecular structures of fungicides benzoicacid and ferimzone contain benzoylhydrazone and pyrimidinehydrazone groups, respectively. People often introduce hydrazones when designing the molecular structure of new fungicides, such as halogenated phenylhydrazones (Organic & Biomolecular Chemistry, 2015, 13(2): 477-486.), acetyl hydrazones (CN 1331080, 2002-01-16) , formyl hydrazone (Journal of Pesticides, 2004, (03): 67-70.) compounds all showed good activity against phytopathogenic fungi.

本发明依据活性亚结构拼接原理，将二卤代吡唑和卤代苯腙引入到同一个分子结构中，设计并合成了一系列结构新颖的二卤代吡唑甲醛的卤代苯腙类化合物，生物活性测定表明，该类化合物对植物病原真菌具有显著的抑制活性。According to the active substructure splicing principle, the present invention introduces dihalogenated pyrazole and halogenated phenylhydrazone into the same molecular structure, and designs and synthesizes a series of halogenated phenylhydrazone compounds of dihalogenated pyrazolecarboxaldehyde with novel structure , the biological activity assay showed that the compounds had significant inhibitory activity against phytopathogenic fungi.

发明内容SUMMARY OF THE INVENTION

本发明的目的在于提供一种二卤代吡唑甲醛的卤代苯腙类化合物。The object of the present invention is to provide a halogenated phenylhydrazone compound of dihalogenated pyrazole carboxaldehyde.

本发明第二个目的在于提供一种二卤代吡唑甲醛的卤代苯腙类化合物的制备方法。The second object of the present invention is to provide a method for preparing a halogenated phenylhydrazone compound of dihalogenated pyrazole carboxaldehyde.

本发明第三个目的在于提供上述化合物的应用。The third object of the present invention is to provide applications of the above compounds.

本发明的第一方面提供了具有通式(I)所示结构的一种二卤代吡唑甲醛的卤代苯腙类化合物，A first aspect of the present invention provides a halogenated phenylhydrazone compound having a structure shown in general formula (I) of a dihalogenated pyrazole carboxaldehyde,

Figure BSA0000176601550000011
Figure BSA0000176601550000011

在式(I)中，所述各个基团具有如下所述的定义：In formula (I), the respective groups have the definitions described below:

X1、X2各自选自一个卤素原子；X 1 and X 2 are each selected from a halogen atom;

Y(n)中，n＝1-5取代，Y(n)选自1-5个卤素原子；In Y (n) , n=1-5 substitution, Y (n) is selected from 1-5 halogen atoms;

R选自氢、C1-6烷基。R is selected from hydrogen, C 1-6 alkyl.

在式(I)中，所述各个基团具有如下所述的优选定义：In formula (I), the respective groups have the preferred definitions as described below:

X1＝X2，选自F、Cl、Br；X 1 =X 2 , selected from F, Cl, Br;

Y(n)中，n＝1-2取代，Y(n)选自1-2个卤素原子，卤素原子选自F、Cl、Br；In Y (n) , n=1-2 substitution, Y (n) is selected from 1-2 halogen atoms, and the halogen atom is selected from F, Cl, Br;

R选自氢、C1-3烷基。R is selected from hydrogen, C 1-3 alkyl.

在式(I)中，所述各个基团具有如下所述的进一步优选定义：In formula (I), the respective groups have further preferred definitions as described below:

X1＝X2，选自Cl；X 1 =X 2 , selected from Cl;

Y(n)选自2-F、4-F、2-Cl、3-Cl、4-Cl、4-Br、2，4-Cl2；Y (n) is selected from 2-F, 4-F, 2-Cl, 3-Cl, 4-Cl, 4-Br, 2,4-Cl2 ;

R选自氢、甲基。R is selected from hydrogen, methyl.

本发明的第二个方面提供了制备式(I)的一种二卤代吡唑甲醛的卤代苯腙类化合物的方法，该方法以式(II)的化合物与式(III)的取代苯肼反应，制备式(I)的一种二卤代吡唑甲醛的卤代苯腙类化合物，其反应方程式可用下述通式(A)表示：A second aspect of the present invention provides a method for preparing a halogenated phenylhydrazone compound of a dihalopyrazole carboxaldehyde of formula (I), the method comprising a compound of formula (II) and a substituted benzene of formula (III) Hydrazine reaction, the halogenated phenylhydrazone compound of a kind of dihalogenated pyrazole carboxaldehyde of the preparation formula (I), its reaction equation can be represented by following general formula (A):

Figure BSA0000176601550000021
Figure BSA0000176601550000021

其中在上述各结构式中：Among the above structural formulas:

X1、X2、Y(n)、R均具有如前所述的相应基团的定义。X 1 , X 2 , Y (n) , R all have the definitions of the corresponding groups as previously described.

本发明的第三个方面涉及式(I)的一种二卤代吡唑甲醛的卤代苯腙类化合物在抑制植物病原真菌和防治植物真菌病害方面的应用，可作为杀菌剂，应用于农药领域。The third aspect of the present invention relates to the application of a halogenated phenylhydrazone compound of a dihalogenated pyrazole carboxaldehyde of formula (I) in inhibiting phytopathogenic fungi and preventing and controlling plant fungal diseases, which can be used as bactericides and applied to pesticides field.

本发明的化合物适合应用于抑制小麦赤霉病菌、草莓灰霉病菌、水稻纹枯病菌。The compound of the present invention is suitable for inhibiting wheat scab, botrytis cinerea and rice sheath blight.

本发明的化合物适合应用于防治小麦赤霉病、草莓灰霉病、水稻纹枯病。The compound of the present invention is suitable for preventing and treating wheat scab, strawberry gray mold and rice sheath blight.

有益效果：Beneficial effects:

1、本发明专利所述的式(I)的一种二卤代吡唑甲醛的卤代苯腙类化合物的分子结构新颖，该结构式含有一个二卤代吡唑基团和卤代苯腙基团，其特点是吡唑通过其4位C原子上的次甲基与腙基团链接。1. The molecular structure of the halogenated phenylhydrazone compound of a kind of dihalogenated pyrazole carboxaldehyde of the formula (I) described in the patent of the present invention is novel, and this structural formula contains a dihalogenated pyrazole group and a halogenated phenylhydrazone group group, which is characterized by a pyrazole linked to a hydrazone group via its methine group on the 4-position C atom.

2、本发明专利所述的式(I)的一种二卤代吡唑甲醛的卤代苯腙类化合物的制备方法简便、原料易得、产率高。2. The preparation method of the halogenated phenylhydrazone compound of a kind of dihalogenated pyrazole carboxaldehyde of the formula (I) described in the patent of the present invention is simple and convenient, the raw materials are readily available, and the yield is high.

3、本发明专利所述的式(I)的一种二卤代吡唑甲醛的卤代苯腙类化合物表现出显著的抑制植物病原真菌的活性，可应用于防治由病原真菌引起的植物病害，具有作为农药杀菌剂的用途。3. The halogenated phenylhydrazone compound of a kind of dihalogenated pyrazole carboxaldehyde of the formula (I) described in the patent of the present invention shows significant activity of inhibiting phytopathogenic fungi, and can be applied to prevent and treat plant diseases caused by pathogenic fungi , with the use of pesticides and fungicides.

具体实施方式Detailed ways

本发明的实质性特点可从下述实施例得以体现，但它不应视为是对本发明的任何限制。The essential features of the present invention can be seen from the following examples, which should not be construed as any limitation to the present invention.

制备实施例Preparation Examples

实施例1：本发明的二卤代吡唑甲醛的卤代苯腙类化合物I-a的制备Embodiment 1: the preparation of the halogenated phenylhydrazone compound I-a of the dihalogenated pyrazole carboxaldehyde of the present invention

在50mL的单口烧瓶中加入15mL乙醇、化合物II-a(3mmol)和2-氯苯肼III-a(3mmol)，1滴乙酸作为催化剂，加热回流2小时，有固体析出，冷却，抽滤，滤饼用少量冰乙醇洗涤两次，干燥，得黄色粉末状固体I-a，其反应方程式如下：15mL of ethanol, compound II-a (3mmol) and 2-chlorophenylhydrazine III-a (3mmol) were added to a 50mL single-necked flask, 1 drop of acetic acid was used as a catalyst, heated to reflux for 2 hours, there was solid precipitation, cooling, suction filtration, The filter cake is washed twice with a small amount of glacial ethanol, and dried to obtain yellow powdery solid I-a, whose reaction equation is as follows:

Figure BSA0000176601550000031
Figure BSA0000176601550000031

采用实施例1的方法，制备了二卤代吡唑甲醛的卤代苯腙类化合物(I)中的I-a～I-n化合物：Using the method of Example 1, I-a～I-n compounds in the halogenated phenylhydrazone compound (I) of dihalopyrazole carboxaldehyde were prepared:

3，5-二氯-4-((2-(2-氯苯基)腙基)甲基)-1H-吡唑(I-a)3,5-Dichloro-4-((2-(2-chlorophenyl)hydrazonyl)methyl)-1H-pyrazole (I-a)

Figure BSA0000176601550000032
Figure BSA0000176601550000032

黄色粉末；收率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.Yellow powder; yield 61.17%; mp225.1-227.8°C; IR (KBr, cm -1 )v: 3310, 3107, 2879, 1597, 1517, 1457, 1291, 1139, 988, 737, 711; 1 H 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); 13 C NMR (100 MHz, 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 C 10 H 7 Cl 3 N 4 ([M+H] + ) 288.9809, found 288.9810.

3，5-二氯-4-((2-(3-氯苯基)腙基)甲基)-1H-吡唑(I-b)3,5-Dichloro-4-((2-(3-chlorophenyl)hydrazonyl)methyl)-1H-pyrazole (I-b)

Figure BSA0000176601550000033
Figure BSA0000176601550000033

黄色粉末；收率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.Yellow powder; yield 65.02%; mp 164.5-167.2°C; IR (KBr, cm -1 ) v: 3321, 3127, 2921, 1596, 1520, 1388, 1244, 1131, 990, 763, 677; 1 H 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=8.2 Hz, 1H), 6.69 (d, J=7.8, 1.2 Hz, 1H); 13 C NMR (100 MHz, 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 C 10 H 7 Cl 3 N 4 ([M+H] + ) 288.9809, found 288.9807.

3，5-二氯-4-((2-(4-氯苯基)腙基)甲基)-1H-吡唑(I-c)3,5-Dichloro-4-((2-(4-chlorophenyl)hydrazonyl)methyl)-1H-pyrazole (I-c)

Figure BSA0000176601550000034
Figure BSA0000176601550000034

灰绿色粉末；收率64.80％；m.p.134.1-135.4℃；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.Gray-green powder; yield 64.80%; mp134.1-135.4°C; IR (KBr, cm -1 )v: 3303, 3131, 2911, 1597, 1516, 1479, 1253, 1132, 991, 797, 634; 1 H 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); 13 C NMR (100 MHz, DMSO-d6) δ: 144.55, 129.39, 127.13, 122.42, 113.63, 110.97; HR-MS (ESI): m/zcalcd for C 10 H 7 Cl 3 N 4 ([M +H] + )288.9809, found 288.9807.

3，5-二氯-4-((2-(2，4-二氯苯基)腙基)甲基)-1H-吡唑(I-d)3,5-Dichloro-4-((2-(2,4-dichlorophenyl)hydrazone)methyl)-1H-pyrazole (I-d)

Figure BSA0000176601550000035
Figure BSA0000176601550000035

白色粉末；收率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.White powder; yield 72.24%; mp237.3-238.8°C; IR (KBr, cm -1 ) v: 3312, 3128, 2913, 1594, 1495, 1374, 1284, 1121, 981, 737, 640; 1 H 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) ; 13 C NMR (100 MHz, 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 C 10 H 6 Cl 4 N 4 ( [M+H] + )324.9390, found 324.9383.

3，5-二氯-4-((2-(2-氟苯基)腙基)甲基)-1H-吡唑(I-e)3,5-Dichloro-4-((2-(2-fluorophenyl)hydrazonyl)methyl)-1H-pyrazole (I-e)

Figure BSA0000176601550000041
Figure BSA0000176601550000041

棕色粉末；收率60.11％；m.p.202.5-204.1℃；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.brown powder; yield 60.11%; mp202.5-204.1°C; IR (KBr, cm -1 ) v: 3315, 3107, 2917, 1625, 1548, 1469, 1387, 1255, 1127, 990, 896, 741; 1 H NMR (400 MHz, DMSO-d6) δ: 14.13 (s, 1H), 10.28 (s, 1H), 8.01 (s, 1H), 7.45 (dd, J=12.0, 4.6 Hz, 1H), 7.17-7.04 ( m, 2H), 6.74 (ddd, J=9.0, 7.6, 1.4 Hz, 1H); 13 C NMR (100 MHz, DMSO-d6) δ: 150.53, 148.16, 133.81 (d, J=9.7 Hz), 129.29, 125.45 (d, J=3.0 Hz), 118.95 (d, J=6.6 Hz), 115.44 (d, J=17.5 Hz), 114.03 (d, J=3.3 Hz), 111.02; HR-MS (ESI): m/ z calcd for C 10 H 7 Cl 2 FN 4 ([M+H] + ) 273.0105, found 273.0094.

3，5-二氯-4-((2-(4-氟苯基)腙基)甲基)-1H-吡唑(I-f)3,5-Dichloro-4-((2-(4-fluorophenyl)hydrazonyl)methyl)-1H-pyrazole (I-f)

Figure BSA0000176601550000042
Figure BSA0000176601550000042

黄色粉末；收率65.37％；m.p.102.3-103.9℃；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.Yellow powder; yield 65.37%; mp 102.3-103.9°C; IR (KBr, cm -1 ) v: 3307, 3123, 2968, 1508, 1389, 1216, 1133, 992, 817, 772, 658; 1 H 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, 4.8 Hz, 2H); 13 C NMR (100 MHz, 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 C 100 H 7 Cl 2 FN 4 ([M+H] + ) 273.0105.found 273.0094.

3，5-二氯-4-((2-(4-溴苯基)腙基)甲基)-1H-吡唑(I-g)3,5-Dichloro-4-((2-(4-bromophenyl)hydrazonyl)methyl)-1H-pyrazole (I-g)

Figure BSA0000176601550000043
Figure BSA0000176601550000043

黄色粉末；收率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.Yellow powder; yield 63.19%; mp 168.8-170.4°C; IR (KBr, cm -1 ) v: 3307, 3131, 2969, 1507, 1388, 1216, 1132, 991, 816, 772, 657; 1 H 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); 13 C NMR (100 MHz, DMSO-d6) δ: 144.92, 132.21, 127.24, 114.15, 110.96, 109.98; HR-MS (ESI): m/z calcd for C 10 H 7 Cl 2 BrN 4 ([M +H] + )334.9280, found 334.9279.

3，5-二氯-4-((2-(2-氯苯基)腙基)甲基)-1-甲基-1H-吡唑(I-h)3,5-Dichloro-4-((2-(2-chlorophenyl)hydrazonyl)methyl)-1-methyl-1H-pyrazole (I-h)

Figure BSA0000176601550000044
Figure BSA0000176601550000044

黄色粉末；收率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.Yellow powder; yield 71.19%; mp 123.5-124.7°C; IR (KBr, cm -1 ) v: 3237, 2984, 2896, 1591, 1537, 1458, 1295, 1244, 1030, 897, 740; 1 H 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); 13 C 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 calcd for C 11 H 9 Cl 3 N 4 ([M+H] + ) 302.9966, found 302.9961.

3，5-二氯-4-((2-(3-氯苯基)腙基)甲基)-1-甲基-1H-吡唑(I-i)3,5-Dichloro-4-((2-(3-chlorophenyl)hydrazonyl)methyl)-1-methyl-1H-pyrazole (I-i)

Figure BSA0000176601550000051
Figure BSA0000176601550000051

黄色粉末；收率67.06％；m.p.151.9-153.6℃；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.Yellow powder; yield 67.06%; mp151.9-153.6°C; IR (KBr, cm -1 ) v: 3257, 2988, 2896, 1592, 1543, 1392, 1241, 1084, 927, 849, 780, 686; 1 H NMR (400 MHz, DMSO-d6) δ: 10.59 (s, 1H), 7.69 (s, 1H), 7.22 (t, J=8.0 Hz, 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); 13 C NMR (100 MHz, 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 for C 11 H 9 Cl 3 N 4 ([M+H] + ) 302.9966, found 302.9961.

3，5-二氯-4-((2-(4-氯苯基)腙基)甲基)-1-甲基-1H-吡唑(I-j)3,5-Dichloro-4-((2-(4-chlorophenyl)hydrazonyl)methyl)-1-methyl-1H-pyrazole (I-j)

Figure BSA0000176601550000052
Figure BSA0000176601550000052

黄色粉末；收率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.Yellow powder; yield 65.20%; mp 159.6-161.8°C; IR (KBr, cm -1 ) v: 3232, 2988, 2896, 1595, 1538, 1408, 1130, 1097, 826, 781; 1 H 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 = 9.9 Hz, 3H); 13 C NMR (100 MHz, 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 C 11 H 9 Cl 3 N 4 ([M+H] + ) 302.9966, found 302.9959.

3，5-二氯-4-((2-(2，4-二氯苯基)腙基)甲基)-1-甲基-1H-吡唑(I-k)3,5-Dichloro-4-((2-(2,4-dichlorophenyl)hydrazone)methyl)-1-methyl-1H-pyrazole (I-k)

Figure BSA0000176601550000053
Figure BSA0000176601550000053

黄色粉末；收率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.Yellow powder; yield 72.62%; mp 170.2-172.1°C; IR (KBr, cm -1 ) v: 3311, 2967, 2901, 1594, 1502, 1388, 1283, 1127, 1048, 807, 770; 1 H 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); 13 C NMR (100 MHz, 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 C 11 H 8 Cl 4 N 4 ([M+H] + ) 338.9547, found 338.9546.

3，5-二氯-4-((2-(2-氟苯基)腙基)甲基)-1-甲基-1H-吡唑(I-l)3,5-Dichloro-4-((2-(2-fluorophenyl)hydrazonyl)methyl)-1-methyl-1H-pyrazole (I-1)

Figure BSA0000176601550000054
Figure BSA0000176601550000054

黄色粉末；收率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.Yellow powder; yield 61.58%; mp 123.3-124.6°C; IR (KBr, cm -1 ) v: 3261, 2984, 2896, 1627, 1543, 1391, 1255, 1125, 1081, 906, 749; 1 H 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, 1.5 Hz, 1H), 3.81 (s, 3H); 13 C NMR (100 MHz, DMSO-d6) δ: 149.40 (d, J=238.9 Hz), 136.10, 133.80 (d, J=9.7 Hz) , 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 C 11 H 9 Cl 2 FN 4 ([M+H] + ) 287.0261, found 287.0255.

3，5-二氯-4-((2-(4-氟苯基)腙基)甲基)-1-甲基-1H-吡唑(I-m)3,5-Dichloro-4-((2-(4-fluorophenyl)hydrazonyl)methyl)-1-methyl-1H-pyrazole (I-m)

Figure BSA0000176601550000061
Figure BSA0000176601550000061

黄色粉末；收率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.Yellow powder; yield 67.23%; mp 141.3-142.6°C; IR (KBr, cm -1 ) v: 3307, 2984, 2901, 1627, 1544, 1499, 1407, 1258, 1066, 818, 772; 1 H 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); 13 C NMR (100 MHz, DMSO-d6) δ: 156.32 (d, J=233.9 Hz), 142.28, 135.81, 126.12, 125.78, 116.09 (d, J=22.4 Hz), 113.13 (d, J = 7.5 Hz), 111.94, 37.05; HR-MS (ESI): m/z calcd for C 11 H 9 Cl 2 FN 4 ([M+H] + ) 287.0261, found 287.0254.

3，5-二氯-4-((2-(4-溴苯基)腙基)甲基)-1-甲基-1H-吡唑(I-n)3,5-Dichloro-4-((2-(4-bromophenyl)hydrazonyl)methyl)-1-methyl-1H-pyrazole (I-n)

Figure BSA0000176601550000062
Figure BSA0000176601550000062

黄色粉末；收率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.Yellow powder; yield 69.96%; mp155.3-157.0°C; IR (KBr, cm -1 ) v: 3232, 2988, 2896, 1590, 1536, 1483, 1408, 1254, 1129, 1129, 889, 775; 1 H NMR (400 MHz, DMSO-d6) δ: 10.53 (s, 1H), 7.68 (s, 1H), 7.36 (d, J=8.8 Hz, 2H), 6.95 (d, J=8.8 Hz, 2H), 3.82 (d, J=6.4 Hz, 3H); 13 CNMR (100 MHz, 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 C 11 H 9 Cl 2 BrN 4 ([M+H] + ) 348.9437, found 348.9429.

用途实施例Example of use

实施例2：本发明的一种二卤代吡唑甲醛的卤代苯腙类化合物(I)的杀菌活性测定Embodiment 2: the bactericidal activity determination of the halogenated phenylhydrazone compound (I) of a kind of dihalogenated pyrazole carboxaldehyde of the present invention

采用菌丝生长速率法测定了一种二卤代吡唑甲醛的卤代苯腙类化合物(I)中的化合物I-a～I-n对3种植物病原菌小麦赤霉病菌(Fusarium graminearum)、草莓灰霉病菌(Botrytis cinerea)、水稻纹枯病菌(Rhizoctonia solani)在10μg/mL浓度下的杀菌活性。The hyphal growth rate method was used to determine the compounds I-a～I-n in the halogenated phenylhydrazone compounds (I) of a dihalogenated pyrazolecarboxaldehyde to three plant pathogens Fusarium graminearum, strawberry botrytis cinerea Bactericidal activity of (Botrytis cinerea), Rhizoctonia solani at a concentration of 10 μg/mL.

测定方法：将13.5mg的待测化合物(包括对照药剂多菌灵)溶解于1.5mL的DMSO中，从中吸取0.1mL溶液，加入0.1mL的DMSO，混合均匀，再从中吸取0.1mL溶液，加入到44.9mL经灭菌的马铃薯葡萄糖琼脂培养基(PDA培养基)中，充分摇匀，制成浓度为10μg/mL的含药培养基，将其倒入3只直径9cm的无菌培养皿中。以加入等量的溶剂制成的培养基为空白对照。同时以加入杀菌剂多菌灵制得的浓度为10μg/mL的培养基为药剂对照。用打孔器(内径0.5cm)将生长正常的菌落打孔制取菌饼，用接种针将菌饼接入上述培养基平板中央，在25℃下于培养箱中倒置培养。待空白对照培养基上的菌落直径长至平板的2/3时测量其直径，每个菌落直径按十字交叉法测量2次，计算其平均值(单位：cm)。各浓度处理和三种对照均设三个重复。计算药剂处理后的生长抑制率，计算公式如下：Determination method: Dissolve 13.5 mg of the test compound (including the control drug carbendazim) in 1.5 mL of DMSO, draw 0.1 mL of the solution from it, add 0.1 mL of DMSO, mix well, and then draw 0.1 mL of the solution from it, add it to the 44.9 mL of sterilized potato dextrose agar medium (PDA medium), shake well to prepare a medicated medium with a concentration of 10 μg/mL, and pour it into three sterile petri dishes with a diameter of 9 cm. The medium prepared by adding the same amount of solvent was used as blank control. At the same time, the medium with the concentration of 10 μg/mL prepared by adding the fungicide carbendazim was used as the drug control. Use a hole puncher (inner diameter of 0.5 cm) to punch the normal growth colonies to prepare a bacterial cake, insert the bacterial cake into the center of the above-mentioned medium plate with an inoculation needle, and cultivate it upside down in an incubator at 25°C. When the diameter of the colony on the blank control medium reaches 2/3 of the plate, the diameter is measured, the diameter of each colony is measured twice by the cross method, and the average value (unit: cm) is calculated. Three replicates were set for each concentration treatment and three controls. To calculate the growth inhibition rate after the drug treatment, the calculation formula is as follows:

计算方法：抑制率(％)＝(溶剂对照菌落直径-处理菌落直径)÷(溶剂对照菌落直径-0.5)×100％Calculation method: inhibition rate (%) = (colony diameter of solvent control - diameter of treated colony) ÷ (colony diameter of solvent control - 0.5) × 100%

测定结果：二卤代吡唑甲醛的卤代苯腙类化合物(I)对3种供试植物病原菌的生长抑制率测定结果列于表1。Determination results: The measurement results of the growth inhibition rate of the halogenated phenylhydrazone compounds (I) of dihalogenated pyrazole carboxaldehyde on the three tested plant pathogens are listed in Table 1.

表1 二卤代吡唑甲醛的卤代苯腙类化合物(I)对3种植物病原菌的抑制率(％，10μg/mL)Table 1 Inhibitory rate (%, 10 μg/mL) of halogenated phenylhydrazone compounds (I) of dihalogenated pyrazolecarboxaldehyde against three phytopathogenic bacteria

Figure BSA0000176601550000071
Figure BSA0000176601550000071

表1显示，二卤代吡唑甲醛的卤代苯腙类化合物(I)中的化合物I-a～I-n在10μg/mL浓度下对3种供试植物病原菌小麦赤霉病菌、草莓灰霉病菌、水稻纹枯病菌具有显著的抑制活性。各化合物对小麦赤霉病菌的抑制率在42.26％～71.92％之间，其中化合物I-b、I-m达到70％以上。各化合物对草莓灰霉病菌的抑制率在46.57％～70.53％之间，其中化合物I-b、I-e达到70％以上。各化合物对水稻纹枯病菌的抑制率在54.04％～70.87％之间，其中化合物I-f、I-n达到70％以上。Table 1 shows that the compounds I-a～I-n in the halogenated phenylhydrazone compounds (I) of dihalogenated pyrazolecarboxaldehyde have a 10 μg/mL concentration against the three tested plant pathogens, S. erythraea, strawberry botrytis cinerea, rice Sheath blight has significant inhibitory activity. The inhibitory rate of each compound against S. cerevisiae was between 42.26% and 71.92%, among which compounds I-b and I-m reached more than 70%. The inhibition rate of each compound against Botrytis cinerea of strawberry was between 46.57% and 70.53%, among which compounds I-b and I-e reached more than 70%. The inhibition rate of each compound against Rhizoctonia solani was between 54.04% and 70.87%, among which compounds I-f and I-n reached more than 70%.

Claims (7)

1. A halogenated benzene hydrazone compound of dihalogenated pyrazole formaldehyde with a structure shown in a formula (I),
Figure FSA0000176601540000011
wherein,
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):
Figure FSA0000176601540000012
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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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114195707A (en) * 2021-12-17 2022-03-18 西北农林科技大学 A class of high-efficiency and broad-spectrum plant antibacterial agent BZ
CN115872933A (en) * 2022-12-30 2023-03-31 中国农业大学 Hydrazone compound containing pyrazole cinnamaldehyde hydrazide and preparation method and application thereof
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

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2933977A (en) * 1976-10-05 1979-04-12 Shell Int Research Aryl hydrazones
US4479953A (en) * 1983-08-25 1984-10-30 Merck & Co., Inc. Pyrazine aldimine compounds as antimicrobial agents
CN1188764A (en) * 1997-01-23 1998-07-29 化学工业部沈阳化工研究院 Pyrazole compounds used as agricultrial germicide and insecticide and acaricide and its preparation
WO1999012910A1 (en) * 1997-09-11 1999-03-18 Nissan Chemical Industries, Ltd. Pyrazole compounds and plant disease control agent
CN1232458A (en) * 1996-09-30 1999-10-20 日本农药株式会社 1,2,3-Thiadiazole derivatives and salts thereof, agricultural and horticultural virus control agents and methods of use thereof
WO1999062335A1 (en) * 1998-06-02 1999-12-09 Nissan Chemical Industries, Ltd. Phenylhydrazine derivative, and commercial antibacterial and antimycotic agent, algicide and agent for preventing attachment of organism comprising the same
US20120302581A1 (en) * 2009-02-13 2012-11-29 Nancy Ratner Methods and Compositions for the Treatment of RAS Associated Disorders

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2933977A (en) * 1976-10-05 1979-04-12 Shell Int Research Aryl hydrazones
US4479953A (en) * 1983-08-25 1984-10-30 Merck & Co., Inc. Pyrazine aldimine compounds as antimicrobial agents
CN1232458A (en) * 1996-09-30 1999-10-20 日本农药株式会社 1,2,3-Thiadiazole derivatives and salts thereof, agricultural and horticultural virus control agents and methods of use thereof
CN1188764A (en) * 1997-01-23 1998-07-29 化学工业部沈阳化工研究院 Pyrazole compounds used as agricultrial germicide and insecticide and acaricide and its preparation
WO1999012910A1 (en) * 1997-09-11 1999-03-18 Nissan Chemical Industries, Ltd. Pyrazole compounds and plant disease control agent
WO1999062335A1 (en) * 1998-06-02 1999-12-09 Nissan Chemical Industries, Ltd. Phenylhydrazine derivative, and commercial antibacterial and antimycotic agent, algicide and agent for preventing attachment of organism comprising the same
US20120302581A1 (en) * 2009-02-13 2012-11-29 Nancy Ratner Methods and Compositions for the Treatment of RAS Associated Disorders

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HWANG, KWANG-JIN 等: "Synthesis and antifungal activities of furoxan derivatives designed as novel fungicide", 《BIOSCIENCE, BIOTECHNOLOGY, AND BIOCHEMISTRY》 *
IBRAHIM M. A.AWAD: "Studies in the Vilsmeier-Haack reaction. Part VII. Synthesis and reaction", 《MONATSHEFTE FUER CHEMIE》 *
JOHNSON, JENNIFER L. 等: "Identification of neutrophil exocytosis Inhibitors (Nexinhibs), small molecule inhibitors of neutrophil exocytosis and inflammation", 《JOURNAL OF BIOLOGICAL CHEMISTRY》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114195707A (en) * 2021-12-17 2022-03-18 西北农林科技大学 A class of high-efficiency and broad-spectrum plant antibacterial agent BZ
CN115872933A (en) * 2022-12-30 2023-03-31 中国农业大学 Hydrazone compound containing pyrazole cinnamaldehyde hydrazide and preparation method and application thereof
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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