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CN111377869B - A kind of halogenated phenylhydrazone compound of dihalogenated pyrazole formaldehyde, preparation method and application thereof - Google Patents

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

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CN111377869B
CN111377869B CN201811616786.4A CN201811616786A CN111377869B CN 111377869 B CN111377869 B CN 111377869B CN 201811616786 A CN201811616786 A CN 201811616786A CN 111377869 B CN111377869 B CN 111377869B
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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
    • C07D231/16—Halogen atoms or nitro radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
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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 formaldehyde, preparation method and the 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 formaldehyde, a preparation method and its application in the prevention and treatment of 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。Halogenated pyrazole is a kind of 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 chlorinated pyrazoles (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.), bromopyrazole-containing amide compounds (Fine Chemical Intermediates, 2007, (03): 27-29.) have fungicidal activity against plant pathogenic fungi. The fungicides furametpyr and penflufen contain chloropyrazole and fluopyrazole respectively, which 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 the fungicides quinone oxime hydrazone (benzoicacid) and pyrimzone (ferimzone) respectively contain benzoyl hydrazone and pyrimidine hydrazone groups. People also often introduce hydrazones when designing the molecular structure of new fungicides, such as introducing halogenated phenylhydrazones (Organic & Biomolecular Chemistry, 2015, 13(2): 477-486.), acetyl hydrazones (CN 1331080, 2002-01-16) , Formylhydrazone (Journal of Pesticide Science, 2004, (03): 67-70.) All exhibit good activity of inhibiting plant pathogenic 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。Based on the principle of active substructure splicing, the present invention introduces dihalogenated pyrazoles and halogenated phenylhydrazones into the same molecular structure, designs and synthesizes a series of halogenated phenylhydrazone compounds with novel structures of dihalogenated pyrazole formaldehyde , biological activity assays show that this type of compound has significant inhibitory activity against plant pathogenic fungi.

发明内容Contents 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 formaldehyde.

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 preparation method of halogenated phenylhydrazone compounds of dihalogenated pyrazole formaldehyde.

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 the application 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，The first aspect of the present invention provides a halogenated phenylhydrazone compound of a dihalogenated pyrazole formaldehyde having a structure represented by general formula (I),

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 as 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 substitutions, Y (n) is selected from 1-2 halogen atoms, and the halogen atoms are 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-Cl 2 ;

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 the preparation of a halogenated phenylhydrazone compound of a dihalogenated pyrazole formaldehyde of formula (I), the method comprises a compound of formula (II) and a substituted benzene of formula (III) Hydrazine reaction, the halogenated phenylhydrazone compound of a kind of dihalogenated pyrazole formaldehyde of preparation formula (I), its reaction equation can represent with following general formula (A):

Figure BSA0000176601550000021
Figure BSA0000176601550000021

其中在上述各结构式中：Wherein in each above-mentioned structural formula:

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) , and R all have the definitions of the corresponding groups as described above.

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 formaldehyde of formula (I) in inhibiting phytopathogenic fungi and preventing and controlling plant fungal diseases. It can be used as a fungicide 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 invention is suitable for inhibiting wheat scab, strawberry gray mold 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 invention is suitable for controlling wheat scab, strawberry gray mold and rice sheath blight.

有益效果：Beneficial effect:

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 a halogenated phenylhydrazone compound of a dihalogenated pyrazole formaldehyde of the formula (I) described in the patent of the present invention is novel, and the structural formula contains a dihalogenated pyrazole group and a halogenated phenylhydrazone group group, which is characterized in that pyrazole is linked to the hydrazone group through the methine group on its 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 a halogenated phenylhydrazone compound of the formula (I) described in the patent of the present invention is simple, 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. A halogenated phenylhydrazone compound of the formula (I) described in the patent of the present invention, which is a dihalogenated pyrazole formaldehyde, exhibits significant activity of inhibiting plant pathogenic fungi, and can be applied to the prevention and treatment of plant diseases caused by pathogenic fungi , has the purposes as pesticide fungicide.

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 substantive features of the present invention can be realized from the following examples, but it should not be regarded as any limitation to the present invention.

制备实施例Preparation Example

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: Preparation of the halogenated phenylhydrazone compound I-a of the dihalogenated pyrazole formaldehyde 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：Add 15mL of ethanol, compound II-a (3mmol) and 2-chlorophenylhydrazine III-a (3mmol) in a 50mL single-necked flask, 1 drop of acetic acid as a catalyst, heat and reflux for 2 hours, solids are precipitated, cooled, suction filtered, The filter cake is washed twice with a small amount of glacial ethanol, and dried to obtain yellow powdery solid I-a, and its 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 compounds (I) of dihalogenated pyrazole formaldehyde 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)hydrazone)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 (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 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)hydrazone)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%; mp164.5-167.2℃; 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=8.2Hz, 1H), 6.69 (d, J=7.8, 1.2Hz, 1H); 13 C 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 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)hydrazone)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℃; 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 (100MHz, 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℃; 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 (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 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)hydrazone)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 (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); 13 C 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 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)hydrazone)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%; mp102.3-103.9°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, 4.8Hz, 2H); 13 C 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 C 10 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)hydrazone)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%; mp168.8-170.4℃; 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 (100MHz, DMSO-d6) δ: 144.92, 132.21, 127.24, 114.15, 110.96, 109.98; HR-MS (ESI): m/z calcd forC 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)hydrazone)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%; mp123.5-124.7℃; 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 calcdfor 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)hydrazone)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 (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); 13 C 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 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)hydrazone)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%; mp159.6-161.8°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 =9.9Hz, 3H); 13 C 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 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%; mp170.2-172.1℃; 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 (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 C 11 H 8 Cl 4 N 4 ([M+H] + )338.9547, found338.9546.

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)hydrazone)methyl)-1-methyl-1H-pyrazole (I-l)

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%; mp123.3-124.6℃; 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, 1.5Hz, 1H), 3.81(s, 3H); 13 C 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 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)hydrazone)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%; mp141.3-142.6℃; 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 (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 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)hydrazone)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℃; IR (KBr, cm -1 ) v: 3232, 2988, 2896, 1590, 1536, 1483, 1408, 1254, 1129, 1129, 889, 775; 1 H 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); 13 CNMR (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 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: Determination of the bactericidal activity of a halogenated phenylhydrazone compound (I) of a dihalogenated pyrazole formaldehyde 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 effect of compound I-a～I-n in a halogenated phenylhydrazone compound (I) of a dihalogenated pyrazole formaldehyde on three kinds of plant pathogenic bacteria wheat scab (Fusarium graminearum) and strawberry gray mold was determined by mycelium growth rate method. (Botrytis cinerea), rice sheath blight (Rhizoctonia solani) fungicidal activity at 10 μg/mL concentration.

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：Assay method: Dissolve 13.5 mg of the compound to be tested (including the reference drug carbendazim) in 1.5 mL of DMSO, draw 0.1 mL of the solution, add 0.1 mL of DMSO, mix well, then draw 0.1 mL of the solution, add to In 44.9 mL of sterilized potato dextrose agar medium (PDA medium), shake well to make a drug-containing medium with a concentration of 10 μg/mL, and pour it into three sterile petri dishes with a diameter of 9 cm. The culture medium prepared by adding the same amount of solvent was used as blank control. At the same time, the medium prepared by adding the fungicide carbendazim with a concentration of 10 μg/mL was used as the drug control. Use a puncher (inner diameter of 0.5 cm) to punch out the normal-growing colonies to prepare bacteria cakes, insert the bacteria cakes into the center of the above medium plate with an inoculation needle, and culture them upside down in an incubator at 25°C. Measure the diameter of the colony on the blank control medium when it reaches 2/3 of the plate, measure the diameter of each colony twice by the cross method, and calculate the average value (unit: cm). Three replicates were set up for each concentration treatment and three controls. 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 (%)=(solvent control colony diameter-treatment colony diameter) ÷ (solvent control colony diameter-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 growth inhibition rate determination results of the halogenated phenylhydrazone compound (I) of dihalogenated pyrazole formaldehyde to three kinds of plant pathogenic bacteria tested 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 of halogenated phenylhydrazone compound (I) of dihalogenated pyrazole formaldehyde to three kinds of plant pathogenic bacteria (%, 10 μg/mL)

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 compound I-a～I-n in the halogenated phenylhydrazone compound (I) of dihalogenated pyrazole formaldehyde is effective to 3 kinds of tested plant pathogenic bacteria wheat scab, strawberry cinerea, rice Rhizoctonia solani has significant inhibitory activity. The inhibitory rate of each compound on wheat head blight is between 42.26% and 71.92%, among which compounds I-b and I-m reach more than 70%. The inhibitory rate of each compound to Botrytis cinerea of strawberry is between 46.57% and 70.53%, among which the compounds I-b and I-e reach more than 70%. The inhibitory rate of each compound on rice sheath blight is between 54.04% and 70.87%, and the compounds I-f and I-n are above 70%.

Claims (6)

1. A halogenated phenylhydrazone compound of dihalogenated pyrazole formaldehyde with a structure shown in a formula (I),
Figure FSB0000201083920000011
wherein,
X 1 、X 2 each selected from a halogen atom;
Y (n) wherein n =1-5 substitution, Y (n) Selected from 1-5 halogen atoms;
r is selected from hydrogen and C 1-6 An alkyl group.
2. The dihalopyrazolecarboxaldehyde halophenylhydrazone compound according to claim 1, characterized in that:
X 1 ＝X 2 selected from F, cl, br;
Y (n) wherein n =1-2 substitution, Y (n) Selected from 1-2 halogen atoms selected from F, cl, br;
r is selected from hydrogen and C 1-3 An alkyl group.
3. The dihalopyrazolecarboxaldehyde halophenylhydrazone compound according to claim 2, characterized in that:
X 1 ＝X 2 selected from Cl;
Y (n) selected from the group consisting of 2-F, 4-F, 2-Cl, 3-Cl, 4-Br, 2,4-Cl 2 ；
R is selected from hydrogen and methyl.
4. 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.
5. The use according to claim 4, 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.
6. The use according to claim 4, 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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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
Identification of neutrophil exocytosis Inhibitors (Nexinhibs), small molecule inhibitors of neutrophil exocytosis and inflammation;Johnson, Jennifer L. 等;《Journal of Biological Chemistry》;20161231;第291卷(第50期);全文 *
Studies in the Vilsmeier-Haack reaction. Part VII. Synthesis and reaction;Ibrahim M. A.Awad;《Monatshefte fuer Chemie》;19901231;第121卷(第12期);全文 *
Synthesis and antifungal activities of furoxan derivatives designed as novel fungicide;Hwang, Kwang-Jin 等;《Bioscience, Biotechnology, and Biochemistry》;19981231;第62卷(第9期);第1694页 *

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