Quinoline hydrazone compound containing hydrazone structure as well as preparation method and application of quinoline hydrazone compound

Abstract

The invention relates to a quinoline hydrazone compound containing a hydrazone structure as well as a preparation method and application of the quinoline hydrazone compound, and relates to the technical field of chemical engineering and pesticides. According to the invention, 5-aminoquinoline is used as a raw material to synthesize a series of quinoline hydrazone compounds containing a hydrazone structure; the prepared compound can effectively prevent and treat plant fungal diseases including cucumber gray mold, potato late blight, sclerotinia rot of colza, tomato gray mold, wheat scab, rice blast, kiwi fruit phomopsis and rice sheath blight disease.

Description

Technical Field

[0001] This invention relates to the fields of chemical technology and pesticide technology, and in particular to a quinoline hydrazone compound containing a hydrazone structure, its preparation method and application. Background Technology

[0002] Tomato gray mold, caused by *Botrytis cinerea* (Bc), is a pre- and post-harvest disease affecting many crops worldwide. Wheat scab, caused by *Fusarium graminearum* (Fg), is a major wheat disease. *Magnaporthe oryzae* (Mo) is the pathogen causing rice blast globally. *Sclerotinia sclerotiorum* (Ss) is a typical necrotic fungal pathogen, primarily causing sclerotinia rot in rapeseed. Late blight of potato, caused by *Phytophthora infestans* (Pi), is one of the most destructive diseases of potatoes worldwide. Gray mold of cucumber, caused by *Botrytis cinerea* (Bc), and rice sheath blight and *Phomopsis* of kiwifruit, caused by *Rhizoctonia solani* (Rs), are also mentioned. Kiwifruit disease caused by *Actinidia kiwifruit* (referred to in this invention as "kiwifruit stem spot disease," or simply "kiwifruit disease") is a notorious agricultural disease worldwide. Once infected, it is difficult to control, causing severe yield and economic losses to crops. Plant fungal diseases are characterized by rapid onset, high damage, and wide distribution. To date, there are no effective chemical agents or other control methods, causing significant losses to agricultural production. There is an urgent need to develop effective agents for control.

[0003] Therefore, finding a highly efficient and environmentally friendly chemical agent to combat plant fungal diseases is an urgent problem to be solved in the field of plant protection. Summary of the Invention

[0004] The purpose of this invention is to provide a quinoline hydrazone compound containing a hydrazone structure, its preparation method, and its application, so as to solve the problems existing in the prior art and provide a compound with significant and green resistance to plant fungal diseases.

[0005] In view of this, one object of the present invention is to provide a quinoline compound containing a hydrazone structure, having the structure shown in general formula A:

[0006]

[0007] Wherein, when X is -CH=, R1 is selected from 3-Trifluoromethyl; 4-Trifluoromethyl; H; 2-Fluoro; 2-Chloro; 2-Bromo; 2-Methyl; -Methyl; 2,4-Dichloro; 2,4-Dimethoxy; 2,4-Bis(trifluoromethyl); 2,5-Dichloro; 3,4-Dimethoxy; 3,5-Dimethoxy-4-hydroxy; 3,5-Bis(trifluoromethyl); 2,6-Difluoro; 2,6-Dichloro;

[0008] When X is -CH=CH-CH=, R1 is selected from any one of 3-Fluoro; 3-Trifluoromethyl; H; 2-Chloro; 2-Nitro; 2-Methoxy; 4-Fluoro; 4-Chloro; 4-Nitro; 4-Methoxy; N,N-Dimethyl.

[0009] Preferably, in the compound structure, X is -CH=CH-CH= and R1 is 3-Fluoro; or X is -CH= and R1 is 3-Trifluoromethyl; or X is -CH= and R1 is 4-Trifluoromethyl; or X is -CH=CH-CH= and R1 is 3-Trifluoromethyl.

[0010] A second objective of this invention is to provide a method for preparing the quinoline compound containing the hydrazone structure, characterized by comprising the following steps:

[0011] (1) 5-aminoquinoline and sodium nitrite were reacted in concentrated hydrochloric acid solution at 0-5℃ to obtain diazotized hydrochloride solution;

[0012] (2) Add ascorbic acid to the diazotized hydrochloride solution, react at 0-5℃, filter, and obtain 5-hydrazinoquinoline hydrochloride;

[0013] (3) The obtained 5-hydrazinoquinoline hydrochloride and sodium bicarbonate were reacted in ethanol solution at room temperature, and then substituted benzaldehyde was added and reacted at room temperature. After separation and purification, target compound 1 was obtained.

[0014]

[0015] Among them, R1 is selected from 3-Trifluoromethyl; 4-Trifluoromethyl; H; 2-Fluoro; 2-Chloro; 2-Bromo; 2-Methyl; 2-Methoxy; 2-Nitro; 4-Fluoro; 4-Chloro; 4-Nitro; hyl; 2,4-Dichloro; 2,4-Dimethoxy; 2,4-Bis(trifluoromethyl); 2,5-Dichloro; 3,4-Dimethoxy; 3,5-Dimethoxy-4-hydroxy; 3,5-Bis(trifluoromethyl); 2,6-Difluoro; 2,6-Dichloro.

[0016] Alternatively, the obtained 5-hydrazinoquinoline hydrochloride and sodium bicarbonate are reacted in ethanol solution at room temperature, followed by the addition of substituted cinnamaldehyde and reaction at room temperature, followed by separation and purification to obtain target compound 2.

[0017]

[0018] R2 is selected from any one of 3-Fluoro; 3-Trifluoromethyl; H; 2-Fluoro; 2-Chloro; 2-Nitro; 2-Methoxy; 4-Fluoro; 4-Chloro; 4-Nitro; 4-Methoxy; N,N-Dimethyl.

[0019] A third objective of this invention is to provide a composition containing the quinoline hydrazone compound with a hydrazone structure as described in claim 1. The composition may further include agricultural adjuvants, fungicides, or insecticides.

[0020] The fourth objective of this invention is to provide the application of the quinoline hydrazone compound containing the hydrazone structure or the composition thereof in the prevention and control of fungal diseases in plants.

[0021] Furthermore, the plant fungal diseases are cucumber gray mold, potato late blight, rapeseed sclerotinia stem rot, tomato gray mold, wheat scab, rice blast, kiwifruit disease, and rice sheath blight, and the effective concentration of the quinoline hydrazone compound containing the hydrazone structure is 0 μg / mL-50 μg / mL, and is not 0 μg / mL.

[0022] The fifth objective of this invention is to provide the application of the quinoline hydrazone compound containing the hydrazone structure or the composition thereof in the preparation of drugs against plant fungal diseases.

[0023] Furthermore, the resistance to plant fungal diseases includes gray mold of cucumber, late blight of potato, sclerotinia stem rot of rapeseed, gray mold of tomato, scab of wheat, rice blast of rice, kiwifruit disease, and rice sheath blight. The effective concentration of the quinoline hydrazone compound containing the hydrazone structure is 0 μg / mL-50 μg / mL, and is not 0 μg / mL.

[0024] The sixth objective of this invention is to provide a method for preventing and controlling plant fungal diseases, by applying the quinoline hydrazone compound containing the hydrazone structure or the composition to the harmful substances of the plant fungal diseases or their living environment.

[0025] Furthermore, the plant fungal diseases are cucumber gray mold, potato late blight, rapeseed sclerotinia stem rot, tomato gray mold, wheat scab, rice blast, kiwifruit disease, and rice sheath blight, and the effective concentration of the quinoline hydrazone compound containing the hydrazone structure is 0 μg / mL-50 μg / mL, and is not 0 μg / mL.

[0026] The quinoline hydrazone compounds of this invention have certain inhibitory effects on agricultural diseases and pests such as tomato gray mold, wheat scab, rice blast, kiwifruit blight, and rice sheath blight. They also have good inhibitory effects on cucumber gray mold, potato late blight, and rapeseed sclerotinia stem rot. They can be used to prepare agents for the preparation of antifungal agents against plant diseases.

[0027] The present invention discloses the following technical effects:

[0028] This invention synthesizes a series of quinoline hydrazone compounds containing hydrazone structures using 5-aminoquinoline as a raw material. The prepared compounds can effectively control plant fungal diseases including cucumber gray mold, potato late blight, rapeseed sclerotinia rot, tomato gray mold, wheat scab, rice blast, kiwifruit disease, and rice sheath blight. Detailed Implementation

[0029] The present invention will be described in detail below with reference to embodiments. These embodiments are for illustrative purposes only and are not intended to limit the scope of application of the present invention. The present invention is not limited to the following embodiments or examples. Any modifications and variations made without departing from the spirit of the present invention should be included within the scope of the present invention. Unless otherwise specified, the experimental materials or reagents used in the following embodiments are commercially available.

[0030] The compounds of the present invention are numbered as shown in Table 1:

[0031] Table 1 Quinoline compounds containing hydrazone structures

[0032]

[0033] Note: A1-A 26In the compound structure, X is -CH=; B1-B 11 In the compound structure, X is -CH=CH-CH=.

[0034] Example 1

[0035] The synthesis of (E)-5-(2-benzylidenehydrazyl)quinoline (compound number A1) includes the following steps:

[0036] (1) 5-aminoquinoline (7.08 g, 48.97 mol, 1 equivalent) and sodium nitrite (4.05 g, 58.76 mol, 1.2 equivalent) were stirred in concentrated hydrochloric acid solution under ice bath conditions for 3 hours to obtain a diazotized hydrochloride solution; this diazotized hydrochloride solution contained intermediate 1 generated, and the reaction was as follows:

[0037]

[0038] (2) Add ascorbic acid (8.62 g, 48.07 mol, 1 equivalent) to the diazotized hydrochloride solution in the ice bath of step (1) and react for 2 hours. Filter to obtain intermediate 2 (5-hydrazinoquinoline hydrochloride).

[0039]

[0040] (3) The intermediate 2(5-hydrazinoquinoline hydrochloride) (0.2 g, 0.862 mol, 1 equivalent) was added to a 50 mL round-bottom flask, and then 10 mL of anhydrous ethanol was added to dissolve it. Sodium bicarbonate (0.181 g, 2.15 mol, 2.5 equivalent) was added under stirring at room temperature. After stirring for five minutes, benzaldehyde (0.109 g, 1.03 mol, 1.2 equivalent) was added. The mixture was reacted at room temperature for 12 hours. Water was added and stirred. The solid was filtered out and dried. The target product A1 was obtained after separation and purification with a yield of 69%.

[0041] Example 2

[0042] The synthesis of (E)-5-(2-(2-fluorobenzyl)hydrazino)quinoline (compound number A2) includes the following steps:

[0043] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0044] (3) Synthesis of (E)-5-(2-(2-fluorobenzyl)hydrazino)quinoline (compound number A2): as in step (3) of Example 1, except that 2-fluorobenzaldehyde was used as the starting material and the yield was 97%.

[0045] Example 3

[0046] The synthesis of (E)-5-(2-(2-chlorobenzyl)hydrazino)quinoline (compound number A3) includes the following steps:

[0047] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0048] (3) Synthesis of (E)-5-(2-(2-chlorobenzyl)hydrazino)quinoline (compound number A3): as in step (3) of Example 1, except that 2-chlorobenzaldehyde was used as the starting material and the yield was 20%.

[0049] Example 4

[0050] The synthesis of (E)-5-(2-(2-bromobenzyl)hydrazino)quinoline (compound number A4) includes the following steps:

[0051] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0052] (3) Synthesis of (E)-5-(2-(2-bromobenzyl)hydrazino)quinoline (compound number A4): as in step (3) of Example 1, except that 2-bromobenzaldehyde was used as the starting material and the yield was 27%.

[0053] Example 5

[0054] The synthesis of (E)-5-(2-(2-methylbenzyl)hydrazino)quinoline (compound number A5) includes the following steps:

[0055] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0056] (3) Synthesis of (E)-5-(2-(2-methylbenzyl)hydrazino)quinoline (compound number A5): as in step (3) of Example 1, except that 2-methylbenzaldehyde was used as the starting material and the yield was 44%.

[0057] Example 6

[0058] The synthesis of (E)-5-(2-(2-methoxybenzyl)hydrazino)quinoline (compound number A6) includes the following steps:

[0059] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0060] (3) Synthesis of (E)-5-(2-(2-methoxybenzyl)hydrazino)quinoline (compound number A6): as in step (3) of Example 1, except that 2-methoxybenzaldehyde was used as the starting material and the yield was 27%.

[0061] Example 7

[0062] The synthesis of (E)-5-(2-(2-nitrobenzylidene)hydrazino)quinoline (compound number A7) includes the following steps:

[0063] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0064] (3) Synthesis of (E)-5-(2-(2-nitrobenzylidene)hydrazino)quinoline (compound number A7): as in step (3) of Example 1, except that 2-nitrobenzaldehyde was used as the starting material and the yield was 47%.

[0065] Example 8

[0066] The synthesis of (E)-5-(2-(4-fluorobenzyl)hydrazino)quinoline (compound number A8) includes the following steps:

[0067] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0068] (3) Synthesis of (E)-5-(2-(4-fluorobenzyl)hydrazino)quinoline (compound number A8): as in step (3) of Example 1, except that 2-fluorobenzaldehyde was used as the starting material and the yield was 96%.

[0069] Example 9

[0070] The synthesis of (E)-5-(2-(4-chlorobenzyl)hydrazino)quinoline (compound number A9) includes the following steps:

[0071] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0072] (3) Synthesis of (E)-5-(2-(4-chlorobenzyl)hydrazino)quinoline (compound number A9): as in step (3) of Example 1, except that 4-chlorobenzaldehyde was used as the starting material and the yield was 98%.

[0073] Example 10

[0074] Synthesis of (E)-5-(2-(4-(trifluoromethyl)benzylidene)hydrazyl)quinoline (compound number A) 10 This includes the following steps:

[0075] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0076] (3) (E)-5-(2-(4-(trifluoromethyl)benzylhydrazine)quinoline (compound number A) 10 Synthesis of ) as in step (3) of Example 1, except that 4-(trifluoromethyl)benzaldehyde is used as the raw material and the yield is 91%.

[0077] Example 11

[0078] Synthesis of (E)-5-(2-(4-nitrobenzylidene)hydrazino)quinoline (compound number A) 11 The process includes the following steps:

[0079] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0080] (3)(E)-5-(2-(4-nitrobenzylidene)hydrazino)quinoline (compound number A) 11 Synthesis of ) as in step (3) of Example 1, except that 4-nitrobenzaldehyde is used as the raw material and the yield is 68%.

[0081] Example 12

[0082] Synthesis of (E)-5-(2-(4-methylbenzyl)hydrazino)quinoline (compound number A) 12 The process includes the following steps:

[0083] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0084] (3) (E)-5-(2-(4-methylbenzyl)hydrazino)quinoline (compound number A) 12 Synthesis of ) as in step (3) of Example 1, except that 4-methylbenzaldehyde is used as the raw material and the yield is 20%.

[0085] Example 13

[0086] Synthesis of (E)-5-(2-(3-fluorobenzyl)hydrazino)quinoline (compound number A) 13 The process includes the following steps:

[0087] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0088] (3)(E)-5-(2-(3-fluorobenzyl)hydrazino)quinoline (compound number A) 13 Synthesis of ) as in step (3) of Example 1, except that 3-fluorobenzaldehyde is used as the raw material and the yield is 59%.

[0089] Example 14

[0090] Synthesis of (E)-5-(2-(3-(trifluoromethyl)benzylidene)hydrazino)quinoline (compound number A) 14 The process includes the following steps:

[0091] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0092] (3)(E)-5-(2-(3-(trifluoromethyl)benzyl)hydrazino)quinoline (compound number A) 14 Synthesis of ) as in step (3) of Example 1, except that 3-(trifluoromethyl)benzaldehyde is used as the raw material and the yield is 51%.

[0093] Example 15

[0094] Synthesis of (E)-5-(2-(3-nitrobenzylidene)hydrazino)quinoline (compound number A) 15 This includes the following steps:

[0095] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0096] (3)(E)-5-(2-(3-nitrobenzylidene)hydrazino)quinoline (compound number A) 15 Synthesis of ) as in step (3) of Example 1, except that 3-nitrobenzaldehyde is used as the raw material and the yield is 52%.

[0097] Example 16

[0098] Synthesis of (E)-5-(2-(3-bromobenzyl)hydrazino)quinoline (compound number A) 16 This includes the following steps:

[0099] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0100] (3) Synthesis of (E)-5-(2-(3-bromobenzyl)hydrazino)quinoline (compound number A) 16 Synthesis of ) as in step (3) of Example 1, except that 3-bromobenzaldehyde is used as the raw material and the yield is 46%.

[0101] Example 17

[0102] Synthesis of (E)-5-(2-(3-methylbenzyl)hydrazino)quinoline (compound number A) 17 This includes the following steps:

[0103] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0104] (3) (E)-5-(2-(3-methylbenzyl)hydrazino)quinoline (compound number A) 17 Synthesis of ) as in step (3) of Example 1, except that 3-methylbenzaldehyde is used as the raw material and the yield is 30%.

[0105] Example 18

[0106] Synthesis of (E)-5-(2-(2,4-dichlorobenzyl)hydrazino)quinoline (compound number A) 18 The process includes the following steps:

[0107] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0108] (3)(E)-5-(2-(2,4-dichlorobenzyl)hydrazino)quinoline (compound number A) 18 Synthesis of ) as in step (3) of Example 1, except that 2,4-dichlorobenzaldehyde is used as the raw material and the yield is 24%.

[0109] Example 19

[0110] Synthesis of (E)-5-(2-(2,4-methoxybenzyl)hydrazino)quinoline (compound number A) 19 The process includes the following steps:

[0111] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0112] (3)(E)-5-(2-(2,4-methoxybenzyl)hydrazino)quinoline (compound number A) 19 Synthesis of ) as in step (3) of Example 1, except that 2,4-methoxybenzaldehyde is used as the raw material and the yield is 26%.

[0113] Example 20

[0114] Synthesis of (E)-5-(2-(2,4-(trifluoromethyl)benzylidene)hydrazyl)quinoline (compound number A) 20 The process includes the following steps:

[0115] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0116] (3) (E)-5-(2-(2,4-(trifluoromethyl)benzyl)hydrazino)quinoline (compound number A) 20 Synthesis of ) as in step (3) of Example 1, except that 2,4-(trifluoromethyl)benzaldehyde is used as the raw material with a yield of 60%.

[0117] Example 21

[0118] Synthesis of (E)-5-(2-(2,5-dichlorobenzyl)hydrazino)quinoline (compound number A) 21 The process includes the following steps:

[0119] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0120] (3)(E)-5-(2-(2,5-dichlorobenzyl)hydrazino)quinoline (compound number A) 21 Synthesis of ) as in step (3) of Example 1, except that 2,5-dichlorobenzaldehyde is used as the raw material and the yield is 58%.

[0121] Example 22

[0122] Synthesis of (E)-5-(2-(3,4-methoxybenzyl)hydrazino)quinoline (compound number A) 22 This includes the following steps:

[0123] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0124] (3) (E)-5-(2-(3,4-methoxybenzyl)hydrazino)quinoline (compound number A) 22 Synthesis of ) as in step (3) of Example 1, except that 3,4-methoxybenzaldehyde is used as the raw material and the yield is 53%.

[0125] Example 23

[0126] Synthesis of (E)-2,6-dimethoxy-4-((2-quinolin-5-yl)hydrazino)methyl)phenol (compound number A) 23 This includes the following steps:

[0127] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0128] (3)(E)-2,6-dimethoxy-4-((2-quinolin-5-yl)hydrazino)methyl)phenol (compound number A) 23 Synthesis of ) as in step (3) of Example 1, except that 3,5-dimethoxy-4-hydroxy-benzaldehyde is used as the raw material and the yield is 23%.

[0129] Example 24

[0130] Synthesis of (E)-5-(2-(3,5-(trifluoromethyl)benzylidene)hydrazino)quinoline (compound number A) 24 This includes the following steps:

[0131] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0132] (3) (E)-5-(2-(3,5-(trifluoromethyl)benzyl)hydrazino)quinoline (compound number A) 24 Synthesis of ) as in step (3) of Example 1, except that 3,5-(trifluoromethyl)benzaldehyde is used as the raw material and the yield is 57%.

[0133] Example 25

[0134] Synthesis of (E)-5-(2-(2,6-difluorobenzyl)hydrazino)quinoline (compound number A) 25 This includes the following steps:

[0135] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0136] (3)(E)-5-(2-(2,6-difluorobenzyl)hydrazino)quinoline (compound number A) 25 Synthesis of ) as in step (3) of Example 1, except that 2,6-difluorobenzaldehyde is used as the raw material and the yield is 88%.

[0137] Example 26

[0138] Synthesis of (E)-5-(2-(2,6-dichlorobenzyl)hydrazino)quinoline (compound number A) 26 This includes the following steps:

[0139] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0140] (3)(E)-5-(2-(2,6-dichlorobenzyl)hydrazino)quinoline (compound number A) 26 Synthesis of ) as in step (3) of Example 1, except that 2,6-dichlorobenzaldehyde is used as the raw material and the yield is 92%.

[0141] Example 27

[0142] The synthesis of (E)-5-(2-((1E,2E)-3-phenylallyl)hydrazino)quinoline (compound number B1) includes the following steps:

[0143] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0144] (3) Synthesis of (E)-5-(2-((1E,2E)-3-phenylenemethyl)hydrazyl)quinoline (compound number B1): as in step (3) of Example 1, except that cinnamaldehyde was used as the starting material and the yield was 97%.

[0145] Example 28

[0146] The synthesis of (E)-5-(2-((1E,2E)-3-(2-chlorophenyl)allyl)hydrazino)quinoline (compound number B2) includes the following steps:

[0147] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0148] (3) Synthesis of (E)-5-(2-((1E,2E)-3-(2-chlorophenyl)allyl)hydrazyl)quinoline (compound number B2): as in step (3) of Example 1, except that 2-chlorocinnamaldehyde was used as the starting material and the yield was 36%.

[0149] Example 29

[0150] The synthesis of (E)-5-(2-((1E,2E)-3-(2-nitrophenyl)allyl)hydrazino)quinoline (compound number B3) includes the following steps:

[0151] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0152] (3) Synthesis of (E)-5-(2-((1E,2E)-3-(2-nitrophenyl)allyl)hydrazyl)quinoline (compound number B3): as in step (3) of Example 1, except that 2-nitrocinnamaldehyde was used as the starting material and the yield was 47%.

[0153] Example 30

[0154] The synthesis of (E)-5-(2-((1E,2E)-3-(2-methoxyphenyl)allyl)hydrazino)quinoline (compound number B4) includes the following steps:

[0155] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0156] (3) Synthesis of (E)-5-(2-((1E,2E)-3-(2-methoxyphenyl)allyl)hydrazyl)quinoline (compound number B4): as in step (3) of Example 1, except that 2-methoxycinnamaldehyde was used as the starting material and the yield was 28%.

[0157] Example 31

[0158] The synthesis of (E)-5-(2-((1E,2E)-3-(4-fluorophenyl)allyl)hydrazino)quinoline (compound number B5) includes the following steps:

[0159] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0160] (3) Synthesis of (E)-5-(2-((1E,2E)-3-(4-fluorophenyl)allyl)hydrazyl)quinoline (compound number B5): as in step (3) of Example 1, except that 4-fluorocinnamaldehyde was used as the starting material and the yield was 46%.

[0161] Example 32

[0162] The synthesis of (E)-5-(2-((1E,2E)-3-(4-chlorophenyl)allyl)hydrazino)quinoline (compound number B6) includes the following steps:

[0163] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0164] (3) Synthesis of (E)-5-(2-((1E,2E)-3-(4-chlorophenyl)allyl)hydrazyl)quinoline (compound number B6): as in step (3) of Example 1, except that 4-chlorocinnamaldehyde was used as the starting material and the yield was 17%.

[0165] Example 33

[0166] The synthesis of (E)-5-(2-((1E,2E)-3-(4-nitrophenyl)allyl)hydrazino)quinoline (compound number B7) includes the following steps:

[0167] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0168] (3) Synthesis of (E)-5-(2-((1E,2E)-3-(4-nitrophenyl)allyl)hydrazyl)quinoline (compound number B7): as in step (3) of Example 1, except that 4-nitrocinnamaldehyde was used as the starting material and the yield was 46%.

[0169] Example 33

[0170] The synthesis of (E)-5-(2-((1E,2E)-3-(4-methoxyphenyl)allyl)hydrazino)quinoline (compound number B8) includes the following steps:

[0171] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0172] (3) Synthesis of (E)-5-(2-((1E,2E)-3-(4-methoxyphenyl)allyl)hydrazyl)quinoline (compound number B8): as in step (3) of Example 1, except that 4-methoxycinnamaldehyde was used as the starting material and the yield was 51%.

[0173] Example 34

[0174] The synthesis of (E)-5-(2-((1E,2E)-3-(3-fluorophenyl)allyl)hydrazino)quinoline (compound number B9) includes the following steps:

[0175] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0176] (3) Synthesis of (E)-5-(2-((1E,2E)-3-(3-fluorophenyl)allyl)hydrazino)quinoline (compound number B9): as in step (3) of Example 1, except that 3-fluorocinnamaldehyde was used as the starting material and the yield was 28%.

[0177] Example 35

[0178] Synthesis of (E)-5-(2-((1E,2E)-3-(3-(trifluoromethyl)phenyl)allyl)hydrazino)quinoline (compound number B) 10 This includes the following steps:

[0179] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0180] (3)(E)-5-(2-((1E,2E)-3-(3-(trifluoromethyl)phenyl)allyl)hydrazyl)quinoline (compound number B) 10 Synthesis of ) as in step (3) of Example 1, except that 3-(trifluoromethyl)cinnamaldehyde is used as the raw material and the yield is 39%.

[0181] Example 36

[0182] Synthesis of N,N-dimethyl-4-((1E,3E)-3-(2-(quinolin-5-yl)prop-1-en-1-yl)aniline (compound number B) 11 This includes the following steps:

[0183] Steps (1) and (2) are the same as steps (1) and (2) in Example 1;

[0184] (3) N,N-dimethyl-4-((1E,3E)-3-(2-(quinolin-5-yl)prop-1-en-1-yl)aniline (compound number B) 11 Synthesis of N,N-dimethylaminocinnamaldehyde: as in step (3) of Example 1, except that N,N-dimethylaminocinnamaldehyde is used as the raw material and the yield is 42%.

[0185] The physicochemical properties and high-resolution mass spectrometry (HRMS) data of quinoline hydrazone compounds containing hydrazone structures are shown in Table 2, and the proton nuclear magnetic resonance (NMR) spectra are also shown. 1 H NMR and carbon spectroscopy 13 The C NMR data are shown in Table 3.

[0186] Table 2. Physicochemical properties of the target compounds and their high-resolution mass spectrometry (HRMS) analysis data.

[0187]

[0188]

[0189] Table 3. 1H NMR spectra of the target compounds ( 1 H NMR and carbon spectrum data 13 (C NMR)

[0190]

[0191]

[0192]

[0193]

[0194]

[0195] Example 1 of effect verification:

[0196] The activity of the target compound in inhibiting tomato gray mold, wheat scab, cucumber gray mold, rice blast, potato late blight, kiwifruit stem spot, rice sheath blight, or rapeseed sclerotinia stem rot was tested in vitro.

[0197] Using the target compound as the agent, the synthesized target compound and commercial drugs pyraclostrobin, quinoline copper, and carbendazim were added to PDA medium to prepare PDA medium with final concentrations of 50 μg / mL of the agent and 0 μg / mL (without the agent) of DMSO. After the plates cooled, the activated plant pathogenic fungi, the prepared drug-containing plates, and the punching device were taken out and placed in a sterilized clean bench. An alcohol lamp was lit to quickly flammate the punching device. After cooling, the activated plant fungi were quickly punched to form 5 mm mycelial discs (colonies with similar growth states were selected to reduce experimental error). Then, the sealing film of the disposable culture dish was torn off and the mouth of the culture dish was quickly flammed. The lid of the culture dish was opened, and the mycelial discs were picked up with the flammed and cooled inoculation needle and inoculated into the culture medium. After labeling, the sealing film was resealed and the culture dish was placed in a fungal incubator for cultivation (fungal incubator temperature: 28℃; cultivation time: 72-96h). Three control groups were repeated for each concentration.

[0198] Colony diameter measurement: After the culture is completed, the diameter (mm) of the colonies is measured using the cross-cross method.

[0199] Calculation of final mycelial growth inhibition rate: Mycelial growth inhibition rate (%) = (Coronation diameter of negative control group - Colony diameter of drug group) / (Coronation diameter of drug group - 0.5) × 100. The final mycelial growth inhibition rate (%) is the average of three replicate control experiments.

[0200] The target compound is effective against pathogenic species of Botrytis cinerea (Bc). bGray mold of cucumber caused by *Rhizoctonia solani* (Rs); sclerotinia stem rot of rice caused by *Rhizoctonia solani* (Ss); fusarium head blight of wheat caused by *Fusarium graminearum* (Fg); rice blast caused by *Oomycetes* (Mo); late blight of potato caused by *Phytophthora infestans* (Pi); *Botrytis cinerea* (Bc) c The antibacterial activity of *Gyromyces hygrophila* (PS) on tomato gray mold and *Actinidia kiwifruit* disease caused by *Ps* is shown in Table 4.

[0201] Table 4. Antimicrobial activity (%) of the target compounds against plant pathogenic fungi. a

[0202]

[0203]

[0204] Note: a The average inhibition rate ± standard deviation, where "\" indicates that the experiment was not performed, b represents cucumber gray mold, and c represents tomato gray mold.

[0205] Antibacterial activity and structure-activity relationship analysis are shown in Table 4. Compounds A1 and A 12 A 14 A 22 A 16 Compounds such as B6 and B8, at a concentration of 50 μg / mL, inhibited the growth of gray mold (Bc) in cucumber. b The inhibition rate of A was over 50%, which was superior to that of the commercial azoxystrobin (68.0%). 10 A 12 A 14 A 22 B9, B 10 The inhibition rates were all 100%, and their activity was comparable to that of quinoline copper and chlorophyll. Compounds A6, A9, and A 10 A 13 A 18 and A 22 At a concentration of 50 μg / mL, these compounds exhibited an inhibition rate of over 50% against rice sheath blight (Rs), superior to the control drug pyraclostrobin (41.9%). Compounds A1, A8, and A... 10 and A 14 Several compounds, at a concentration of 50 μg / mL, showed an inhibition rate of over 50% against Sclerotinia sclerotinia (Ss) in rapeseed, which was superior to the control drug azoxystrobin (54.3%). Compound A was particularly effective. 14 The inhibition rate was 100%, superior to the commercial drug quinoline copper, and its activity was comparable to that of rust-reducing agents. Compound B 10At 50 μg / mL, it exhibited superior antifungal activity against wheat scab (Fg) compared to the control drug pyraclostrobin (38.0%). Compounds A3 and A... 10 A 14 B1 and B 10 At 50 μg / mL, the antibacterial activity against rice blast (Mo) was superior to the control drug pyraclostrobin (41.9%), among which compound A... 14 Its activity is comparable to that of quinoline copper (73.4%). Compounds A10, A12, A14, B5, B8, and B... 10 Several compounds, at a concentration of 50 μg / mL, showed superior antibacterial activity against potato late blight (Pi) compared to three commercial drugs: azoxystrobin (56.3%), quinoline copper (15.1%), and carbendazim (10.8%). Compounds A1, A6, A8, and A... 10 A 13 A 14 B5, B8, B 10 and B 11 Several compounds at 50 μg / mL inhibited the activity of Botrytis cinerea (Bc.) on tomatoes. c The inhibition rates of these compounds were all superior to those of the commercial azoxystrobin (17.9%). Compounds A1, A2, and A... 10 A 12 A 13 A 22 B1, B4 and B 10 Several compounds, at a concentration of 50 μg / mL, showed superior inhibition rates against *Pseudomonas kiwifruit* (Ps) compared to the commercial azoxystrobin (21.9%). Among these, compounds A1, A2, and A... 10 A 13 A 14 A 22 B4 and B 10 The inhibition rate against Ps (a type of fungus) in kiwifruit was better than that of quinoline copper (62.2%).

[0206] Different substituent groups R, the positions of groups on the R-benzene ring, and chain length X result in varying antifungal activities against plant pathogenic fungi in quinoline hydrazone compounds containing hydrazone structures, with some showing significant differences. For example, at a concentration of 50 μg / mL, the target compound exhibits different antifungal activities against cucumber gray mold (Bc). b The antibacterial activities showed significant differences: (1) When the substituent R was different, the order of activity was as follows: A 12 (100%, 4-Methyl) = A 10 (100%, 4-Trifluoromethyl)>A9 (60.7%, 4-Chloro)>A 11(42.6%, 4-Nitro) > A8 (25.8%, 4-Fluoro), indicating a significant difference in antibacterial activity. When the substituent is Trifluoromethyl, the compound exhibits broad-spectrum fungicidal effects against plant fungi. (2) The antibacterial activity varies significantly depending on the position of the R-substituted benzene ring substituent: when the R-substituted benzene ring substituent is CH3, the activity is optimal when located at position 4 of the benzene ring. A 12 (100%, 4-Methyl)>A5 (21.5%, 2-Methyl)>A 17 (19.9%, 3-Methyl). (3) When the R substituent positions of compounds are the same, the antibacterial activity of compounds is affected by the chain length X. For example, B9 (100%, 3-Fluoro) > A. 13 (0.5%, 3-Fluoro). When X is -CH=CH-CH= and R1 is 3-Fluoro, the antibacterial effect is significantly enhanced compared to when X is -CH= and R1 is 3-Fluoro. When X is -CH= and R1 is 4-Trifluoromethyl or 3-Trifluoromethyl; or when X is -CH=CH-CH= and R1 is 3-Trifluoromethyl, it has good broad-spectrum antibacterial activity against plant pathogenic fungi.

[0207] In summary, the quinoline hydrazone compounds containing hydrazone structures of the present invention have broad-spectrum fungicidal effects on plant fungi and can be used to prevent and control plant fungal diseases.

[0208] The conventional techniques and solutions not described in detail in the above embodiments are all well known in the art, and therefore will not be elaborated upon here. The above embodiments and / or experimental examples describe the preferred embodiments of the present invention in detail. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, and these simple modifications all fall within the protection scope of the present invention.

Claims

1. A quinoline compound containing a hydrazone structure, characterized in that, It has the structure shown in general formula A: Wherein, when X is -CH=, R1 is selected from 3-Trifluoromethyl; 4-Trifluoromethyl; H; 2-Fluoro; 2-Chloro; 2-Bromo; 2-Methyl; -Methyl; 2,4-Dichloro; 2,4-Dimethoxy; 2,4-Bis(trifluoromethyl); 2,5-Dichloro; 3,4-Dimethoxy; 3,5-Dimethoxy-4-hydroxy; 3,5-Bis(trifluoromethyl); 2,6-Difluoro; 2,6-Dichloro; When X is -CH=CH-CH=, R1 is selected from any one of 3-Fluoro; 3-Trifluoromethyl; H; 2-Chloro; 2-Nitro; 2-Methoxy; 4-Fluoro; 4-Chloro; 4-Nitro; 4-Methoxy; N,N-Dimethyl.

2. The compound according to claim 1, characterized in that, X is -CH=CH-CH=, R1 is 3-Fluoro; or X is -CH=, R1 is 3-Trifluoromethyl; or X is -CH=, R1 is 4-Trifluoromethyl; or X is -CH=CH-CH=, R1 is 3-Trifluoromethyl.

3. The method for preparing the quinoline compound containing a hydrazone structure according to claim 1, characterized in that, Includes the following steps: (1) 5-aminoquinoline and sodium nitrite were reacted in concentrated hydrochloric acid solution at 0-5℃ to obtain diazotized hydrochloride solution; (2) Add ascorbic acid to the diazotized hydrochloride solution, react at 0-5℃, filter, and obtain 5-hydrazinoquinoline hydrochloride; (3) The obtained 5-hydrazinoquinoline hydrochloride and sodium bicarbonate were reacted in ethanol solution at room temperature, and then substituted benzaldehyde was added and reacted at room temperature. After separation and purification, target compound 1 was obtained. Among them, R1 is selected from 3-Trifluoromethyl; 4-Trifluoromethyl; H; 2-Fluoro; 2-Chloro; 2-Bromo; 2-Methyl; 2-Methoxy; 2-Nitro; 4-Fluoro; 4-Chloro; 4-Nitro; hyl; 2,4-Dichloro; 2,4-Dimethoxy; 2,4-Bis(trifluoromethyl); 2,5-Dichloro; 3,4-Dimethoxy; 3,5-Dimethoxy-4-hydroxy; 3,5-Bis(trifluoromethyl); 2,6-Difluoro; 2,6-Dichloro. Alternatively, the obtained 5-hydrazinoquinoline hydrochloride and sodium bicarbonate are reacted in ethanol solution at room temperature, followed by the addition of substituted cinnamaldehyde and reaction at room temperature. After separation and purification, the target compound 2 is obtained. R2 is selected from any one of 3-Fluoro; 3-Trifluoromethyl; H; 2-Fluoro; 2-Chloro; 2-Nitro; 2-Methoxy; 4-Fluoro; 4-Chloro; 4-Nitro; 4-Methoxy; N,N-Dimethyl.

4. A composition, characterized in that, The compound containing the quinoline hydrazone structure as described in claim 1.

5. The use of the quinoline hydrazone compound containing a hydrazone structure as described in claim 1 or the composition as described in claim 4 in the prevention and control of fungal diseases in plants.

6. The application as described in claim 5, characterized in that, The plant fungal diseases mentioned are cucumber gray mold, potato late blight, rapeseed sclerotinia stem rot, tomato gray mold, wheat scab, rice blast, kiwifruit disease, and rice sheath blight. The effective concentration of the quinoline hydrazone compound containing the hydrazone structure is 0 μg / mL-50 μg / mL, and is not 0 μg / mL.

7. The use of the quinoline hydrazone compound containing a hydrazone structure as described in claim 1 or the composition as described in claim 3 in the preparation of drugs against plant fungal diseases.

8. The application as described in claim 7, characterized in that, The plant fungal diseases mentioned are cucumber gray mold, potato late blight, rapeseed sclerotinia stem rot, tomato gray mold, wheat scab, rice blast, kiwifruit disease, and rice sheath blight. The effective concentration of the quinoline hydrazone compound containing the hydrazone structure is 0 μg / mL-50 μg / mL, and is not 0 μg / mL.

9. A method for controlling fungal diseases of plants, characterized in that, The quinoline hydrazone compound containing the hydrazone structure of claim 1 or the composition of claim 3 is applied to the harmful substances of the plant fungal disease or its living environment.

10. The method as described in claim 9, characterized in that, The plant fungal diseases mentioned are cucumber gray mold, potato late blight, rapeseed sclerotinia stem rot, tomato gray mold, wheat scab, rice blast, kiwifruit disease, and rice sheath blight. The effective concentration of the quinoline hydrazone compound containing the hydrazone structure is 0 μg / mL-50 μg / mL, and is not 0 μg / mL.

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