WO2021168903A1 - S-substituted-thiosemicarbazone structure compound and preparation method and application thereof - Google Patents

Abstract

Provided are an S-substituted-thiosemicarbazone structure compound shown in a formula I and a preparation method and an application thereof. The S-substituted-thiosemicarbazone compound shown in the formula I has an excellent prevention and treatment effect on agricultural common pathogenic bacteria, has better performance than the existing positive drug azoxystrobin in in-vitro and in-vivo tests, and has the potential of replacing or supplementing existing bactericide in the existing market.

Description

S-substituted-thiosemicarbazone structure compound and preparation method and application thereof

This application requires that it be filed with the State Intellectual Property Office of China on February 28, 2020. The patent application number is 202010130869.3, and the title of the invention is "an S-substituted-thiosemicarbazone structure compound and its preparation method and application." priority. The full text of this application is incorporated into this application by reference.

Technical field

The invention belongs to the field of chemical technology, and specifically relates to an S-substituted-thiosemicarbazone structure compound and a preparation method and application thereof.

Background technique

In modern agricultural production, fungicides are of great significance to protect crops from plant diseases, reduce disease losses, and increase crop quality. However, with the widespread use of fungicides, the problem of drug resistance has become more and more prominent. The large-scale and long-term use of fungicides in the pesticide market have shown different degrees of resistance, and their control of existing pathogens has declined. Significantly.

Therefore, the development of new structures and fungicides sensitive to existing pathogens is of great significance to current agricultural production.

Summary of the invention

In order to improve the above technical problems, the present invention provides an S-substituted-thiosemicarbazone structure compound represented by formula I and a salt thereof,

in,

R ^{1 is} selected from H, C ₁ -C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, C ₁ -C ₁₂ alkoxycarbonyl, C ₁ -C ₁₂ alkoxy C ₁ -C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkoxy C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkyl sulfide C ₁ -C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkylthio C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxycarbonyl C ₁ -C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkoxycarbonyl C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkylthiocarbonyl C ₁ -C ₁₂ alkyl group, halo C ₁ -C ₁₂ alkylthiocarbonyl C ₁ -C ₁₂ alkyl group;

R ^{2 is} selected from H, halogen, hydroxyl, amino, nitro, cyano, carboxy, C ₁ -C ₁₂ alkyl, halo C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, halo C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₂ cycloalkyl, -OC ₃ -C ₁₂ cycloalkyl, C ₁ -C ₁₂ alkylamino, halogenated C ₁ -C ₁₂ alkylamino, two (C _1- C ₁₂ alkyl)amino, -NHC ₃ -C ₁₂ cycloalkyl, halogenated di(C ₁ -C ₁₂ alkyl)amino, di(C ₁ -C ₁₂ alkyl)aminocarbonyl, C ₁ -C ₁₂ alkylthio, -SC ₃ -C ₁₂ cycloalkyl, halogenated C ₁ -C ₁₂ alkylthio, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, C ₂ -C ₁₂ alkenyloxy , Halogenated C ₂ -C ₁₂ alkenyloxy, C ₂ -C ₁₂ alkynyloxy, halogenated C ₂ -C ₁₂ alkynyloxy, C ₁ -C ₁₂ alkylsulfonyl, halogenated C ₁ -C ₁₂ alkane Sulfonyl, C ₁ -C ₁₂ alkylcarbonyl, -OCOC ₁ -C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkylcarbonyl, C ₁ -C ₁₂ alkoxycarbonyl, halogenated C ₁ -C ₁₂ Alkoxycarbonyl, C ₁ -C ₁₂ alkoxy C ₁ -C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkoxy C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkylthio C _1- C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkylthio C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxycarbonyl C ₁ -C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkoxy Carbonyl C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkylthiocarbonyl C ₁ -C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkylthiocarbonyl C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ Alkylcarbonyloxy, halogenated C ₁ -C ₁₂ alkylcarbonyloxy, C ₁ -C ₁₂ alkoxycarbonyloxy, halogenated C ₁ -C ₁₂ alkoxycarbonyloxy, C ₁ -C ₁₂ Alkylsulfonyloxy, halogenated C ₁ -C ₁₂ alkylsulfonyloxy, C ₁ -C ₁₂ alkoxy C ₁ -C ₁₂ alkoxy or halogenated C ₁ -C ₁₂ alkoxy C ₁ -C ₁₂ alkoxy;

The number of R ² substituents can be 1-5, and when it is 1-5, each R ² substituent is the same or different.

According to an embodiment of the present invention, R ^{1 is} selected from H, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylthio C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkylthio C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxycarbonyl C ₁ -C ₆ alkyl , Halogenated C ₁ -C ₆ alkoxycarbonyl C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylthiocarbonyl C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkylthiocarbonyl C ₁ -C ₆ alkyl;

R ^{2 is} selected from H, halogen, hydroxyl, amino, nitro, cyano, carboxy, C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halo C ₁ -C ₆ alkoxy, C ₃ -C ₆ cycloalkyl, -OC ₃ -C ₆ cycloalkyl, C ₁ -C ₆ alkylamino, halogenated C ₁ -C ₆ alkylamino, two (C _1- C ₆ alkyl) amino, -NHC ₃ -C ₆ cycloalkyl, halogenated bis (C ₁ -C ₆ alkyl) amino, bis (C ₁ -C ₆ alkyl) amino carbonyl, C ₁ -C ₆ alkylthio, -SC ₃ -C ₆ cycloalkyl, halogenated C ₁ -C ₆ alkylthio, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ alkenyloxy , Halogenated C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ alkynyloxy, halogenated C ₂ -C ₆ alkynyloxy, C ₁ -C ₆ alkylsulfonyl, halogenated C ₁ -C ₆ alkane Sulfonyl, C ₁ -C ₆ alkylcarbonyl, -OCOC ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl, halogenated C ₁ -C ₆ Alkoxycarbonyl, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylthio C _1- C ₆ alkyl, halogenated C ₁ -C ₆ alkylthio C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxycarbonyl C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkoxy Carbonyl C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylthiocarbonyl C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkylthiocarbonyl C ₁ -C ₆ alkyl, C ₁ -C ₆ Alkylcarbonyloxy, halogenated C ₁ -C ₆ alkylcarbonyloxy, C ₁ -C ₆ alkoxycarbonyloxy, halogenated C ₁ -C ₆ alkoxycarbonyloxy, C ₁ -C ₆ Alkylsulfonyloxy, halogenated C ₁ -C ₆ alkylsulfonyloxy, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkoxy or halogenated C ₁ -C ₆ alkoxy C ₁ -C ₆ alkoxy;

The number of R ² substituents can be 1 to 4, and when it is 1 to 4, each R ² substituent is the same or different.

According to an embodiment of the present invention, R ^{1 is} selected from H, C ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₁ -C ₃ alkoxycarbonyl, C ₁ -C ₃ alkoxy C ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ alkoxy C ₁ -C ₃ alkyl, C ₁ -C ₃ alkylthio C ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ alkylthio C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxycarbonyl C ₁ -C ₃ alkyl , Halogenated C ₁ -C ₃ alkoxycarbonyl C ₁ -C ₃ alkyl, C ₁ -C ₃ alkylthiocarbonyl C ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ alkylthiocarbonyl C ₁ -C ₃ alkyl;

R ^{2 is} selected from H, halogen, hydroxyl, amino, nitro, cyano, carboxy, C ₁ -C ₃ alkyl, halo C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, halo C ₁ -C ₃ alkoxy, C ₃ -C ₆ cycloalkyl, -OC ₃ -C ₄ cycloalkyl, C ₁ -C ₃ alkylamino, halogenated C ₁ -C ₃ alkylamino, two (C _1- C ₃ alkyl)amino, -NHC ₃ -C ₄ cycloalkyl, halogenated di(C ₁ -C ₃ alkyl)amino, di(C ₁ -C ₃ alkyl)aminocarbonyl, C ₁ -C ₃ alkylthio, -SC ₃ -C ₄ cycloalkyl, halogenated C ₁ -C ₃ alkylthio, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₂ -C ₄ alkenyloxy , Halogenated C ₂ -C ₄ alkenyloxy, C ₂ -C ₄ alkynyloxy, halogenated C ₂ -C ₄ alkynyloxy, C ₁ -C ₃ alkylsulfonyl, halogenated C ₁ -C ₃ alkane Sulfonyl, C ₁ -C ₃ alkylcarbonyl, -OCOC ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ alkylcarbonyl, C ₁ -C ₃ alkoxycarbonyl, halogenated C ₁ -C ₃ Alkoxycarbonyl, C ₁ -C ₃ alkoxy C ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ alkoxy C ₁ -C ₃ alkyl, C ₁ -C ₃ alkylthio C _1- C ₃ alkyl, halogenated C ₁ -C ₃ alkylthio C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxycarbonyl C ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ alkoxy Carbonyl C ₁ -C ₃ alkyl, C ₁ -C ₃ alkylthiocarbonyl C ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ alkylthiocarbonyl C ₁ -C ₃ alkyl, C ₁ -C ₃ Alkylcarbonyloxy, halogenated C ₁ -C ₃ alkylcarbonyloxy, C ₁ -C ₃ alkoxycarbonyloxy, halogenated C ₁ -C ₃ alkoxycarbonyloxy, C ₁ -C ₃ Alkylsulfonyloxy, halogenated C ₁ -C ₃ alkylsulfonyloxy, C ₁ -C ₃ alkoxy C ₁ -C ₃ alkoxy or halogenated C ₁ -C ₃ alkoxy C ₁ -C ₃ alkoxy;

The number of R ² substituents can be 1, 2, 3, or 4, and when it is 1 to 4, each R ² substituent is the same or different.

According to an embodiment of the present invention, R ^{1 is} selected from H, C ₁ -C ₃ alkyl;

R ^{2 is} selected from H, halogen, hydroxyl, amino, nitro, cyano, carboxy, C ₁ -C ₃ alkyl, halo C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, halo C ₁ -C ₃ alkoxy, C ₃ -C ₆ cycloalkyl, -OC ₃ -C ₄ cycloalkyl, C ₁ -C ₃ alkylamino, halogenated C ₁ -C ₃ alkylamino, two (C _1- C ₃ alkyl)amino, -NHC ₃ -C ₄ cycloalkyl, halogenated di(C ₁ -C ₃ alkyl)amino, di(C ₁ -C ₃ alkyl)aminocarbonyl, C ₁ -C ₃ alkoxycarbonyl group, a halo-C ₁ -C ₃ alkoxycarbonyl, C ₁ -C ₃ alkylcarbonyloxy, halo-C ₁ -C ₃ alkylcarbonyloxy, -SC ₃ -C ₄ cycloalkyl Group, -COOC ₁ -C ₃ alkyl, -OCOC ₁ -C ₃ alkyl.

According to a preferred embodiment of the present invention, R ^{1 is} selected from H, methyl;

R ^{2 is} selected from H, fluorine, chlorine, bromine, hydroxyl, nitro, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy, dimethylamino, methoxycarbonyl, methylcarbonyl Oxy.

According to a preferred embodiment of the present invention, R ^{1 is} selected from H, methyl;

R ^{2 is} selected from H, 2-nitro, 3-nitro, 4-nitro, 2-methyl, 3-methyl, 4-methyl, 2-methoxy, 3-methoxy, 4- Methoxy, 2-fluoro, 3-fluoro, 4-fluoro, 2-chloro, 3-chloro, 4-chloro, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2 -Trifluoromethoxy, 3-trifluoromethoxy, 4-trifluoromethoxy, 4chloro-2-fluoro, 3,4-dimethyl, 2,4-difluoro, 3,4,5 -Trifluoro, 2-fluoro-5-trifluoromethyl, 2,4,6-trifluoro, 2,4,5-trifluoro, 2,3,4-trifluoro, 3,4-difluoro, 3 -Trifluoromethyl-4-fluoro, 4-hydroxy, 2,4-dihydroxy, 3,4-dimethoxy, 4-fluoro-3-cyano, 2,4-dimethoxy, 3- Hydroxy, 3-hydroxy-4-methoxy, 3,4-dimethoxy, 3-methyl-4-fluoro.

According to a preferred embodiment of the present invention, R ^{1 is} selected from H;

R ^{2 is} selected from H, 2-nitro, 3-nitro, 4-nitro, 2-methyl, 3-methyl, 4-methyl, 2-methoxy, 3-methoxy, 4- Methoxy, 2-fluoro, 3-fluoro, 4-fluoro, 2-chloro, 3-chloro, 4-chloro, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2 -Trifluoromethoxy, 3-trifluoromethoxy, 4-trifluoromethoxy, 2,4-difluoro, 3,4,5-trifluoro, 2-fluoro-5-trifluoromethyl, 2,4,6 trifluoro, 2,4,5-trifluoro, 2,3,4-trifluoro, 3,4-difluoro, 3-trifluoromethyl-4-fluoro, 4-hydroxy, 2, 4-dihydroxy, 3,4-dimethoxy, 4-fluoro-3-cyano, 2,4-dimethoxy, 3-hydroxy, 3-hydroxy-4-methoxy, 3,4- Dimethoxy

According to a preferred embodiment of the present invention, R ^{1 is} selected from methyl;

R ^{2 is} selected from H, 4-nitro, 3-methyl, 3-trifluoromethyl, 4chloro-2-fluoro, 3,4-dimethyl, 2,4-difluoro, 4-hydroxy, 2 , 4-Dihydroxy, 2-chloro, 3-methyl-4-fluoro, 4-methyl, 3-chloro, 2-fluoro, 4-methyl, 4-chloro.

According to a preferred embodiment of the present invention, R ^{1 is} selected from H;

R ^{2 is} selected from 4-chloro.

According to an embodiment of the present invention, the salt of the S-substituted-thiosemicarbazone compound represented by formula I is selected from its hydrochloride, sulfate, hydrobromide, methanesulfonate, citrate, and oxalic acid Salt, succinate, maleate, citrate, acetate, lactate, phosphate, hydroiodide, nitrate, tartrate, p-toluenesulfonate, etc.

According to a preferred embodiment of the present invention, R ^{1 is} selected from the following groups:

R ^{2 is} selected from the following groups:

in,

Where is the connection site.

As an example, the S-substituted-thiosemicarbazone compound represented by formula I is selected from the following compounds,

table 3:

Compound number	R 1	R 2
3-1	H	H
3-2	H	2-F
3-3	H	3-F
3-4	H	4-F
3-5	H	2,3-F
3-6	H	2,4-F
3-7	H	2,5-F
3-8	H	2,6-F
3-9	H	3,4-F
3-10	H	3,5-F
3-11	H	2,3,4-F
3-12	H	2,3,5-F
3-13	H	2,3,6-F
3-14	H	2,4,5-F
3-15	H	2,4,6-F
3-16	H	3,4,5-F
3-17	H	2-Cl
3-18	H	3-Cl
3-19	H	4-Cl
3-20	H	2,3-Cl
3-21	H	2,4-Cl
3-22	H	2,5-Cl
3-23	H	2,6-Cl
3-24	H	3,4-Cl

3-25	H	3,5-Cl
3-26	H	2,3,4-Cl
3-27	H	2,3,5-Cl
3-28	H	2,3,6-Cl
3-29	H	2,4,5-Cl
3-30	H	2,4,6-Cl
3-31	H	3,4,5-Cl
3-32	H	2-Br
3-33	H	3-Br
3-34	H	4-Br
3-35	H	2,3-Br
3-36	H	2,4-Br
3-37	H	2,5-Br
3-38	H	2,6-Br
3-39	H	3,4-Br
3-40	H	3,5-Br
3-41	H	2,3,4-Br
3-42	H	2,3,5-Br
3-43	H	2,3,6-Br
3-44	H	2,4,5-Br
3-45	H	2,4,6-Br
3-46	H	3,4,5-Br
3-47	H	2-I
3-48	H	3-I
3-49	H	4-I
3-50	H	2,3-I
3-51	H	2,4-I
3-52	H	2,5-I
3-53	H	2,6-I
3-54	H	3,4-I
3-55	H	3,5-I
3-56	H	2,3,4-I
3-57	H	2,3,5-I
3-58	H	2,3,6-I
3-59	H	2,4,5-I
3-60	H	2,4,6-I
3-61	H	3,4,5-I
3-62	H	2-CH 3
3-63	H	3-CH 3
3-64	H	4-CH 3
3-65	H	2,3-CH 3
3-66	H	2,4-CH 3
3-67	H	2,5-CH 3

3-68	H	2,6-CH 3
3-69	H	3,4-CH 3
3-70	H	3,5-CH 3
3-71	H	2,3,4-CH 3
3-72	H	2,3,5-CH 3
3-73	H	2,3,6-CH 3
3-74	H	2,4,5-CH 3
3-75	H	2,4,6-CH 3
3-76	H	3,4,5-CH 3
3-77	H	2-OCH 3
3-78	H	3-OCH 3
3-79	H	4-OCH 3
3-80	H	2,3-OCH 3
3-81	H	2,4-OCH 3
3-82	H	2,5-OCH 3
3-83	H	2,6-OCH 3
3-84	H	3,4-OCH 3
3-85	H	3,5-OCH 3
3-86	H	2,3,4-OCH 3
3-87	H	2,3,5-OCH 3
3-88	H	2,3,6-OCH 3
3-89	H	2,4,5-OCH 3
3-90	H	2,4,6-OCH 3
3-91	H	3,4,5-OCH 3
3-92	H	2-CN
3-93	H	3-CN
3-94	H	4-CN
3-95	H	2,3-CN
3-96	H	2,4-CN
3-97	H	2,5-CN
3-98	H	2,6-CN
3-99	H	3,4-CN
3-100	H	3,5-CN
3-101	H	2-NO 2
3-102	H	3-NO 2
3-103	H	4-NO 2
3-104	H	2,3-NO 2
3-105	H	2,4-NO 2
3-106	H	2,5-NO 2
3-107	H	2,6-NO 2
3-108	H	3,4-NO 2
3-109	H	3,5-NO 2
3-110	H	2-OH

3-111	H	3-OH
3-112	H	4-OH
3-113	H	2,3-OH
3-114	H	2,4-OH
3-115	H	2,5-OH
3-116	H	2,6-OH
3-117	H	3,4-OH
3-118	H	3,5-OH
3-119	H	2-CF 3
3-120	H	3-CF 3
3-121	H	4-CF 3
3-122	H	2,3-CF 3
3-123	H	2,4-CF 3
3-124	H	2,5-CF 3
3-125	H	2,6-CF 3
3-126	H	3,4-CF 3
3-127	H	3,5-CF 3
3-128	H	2-OCF 3
3-129	H	3-OCF 3
3-130	H	4-OCF 3
3-131	H	2,3-OCF 3
3-132	H	2,4-OCF 3
3-133	H	2,5-OCF 3
3-134	H	2,6-OCF 3
3-135	H	3,4-OCF 3
3-136	H	3,5-OCF 3
3-137	H	2-OCOCH 3
3-138	H	3-OCOCH 3
3-139	H	4-OCOCH 3
3-140	H	2,3-OCOCH 3
3-141	H	2,4-OCOCH 3
3-142	H	2,5-OCOCH 3
3-143	H	2,6-OCOCH 3
3-144	H	3,4-OCOCH 3
3-145	H	3,5-OCOCH 3
3-146	H	2-COOCH 3
3-147	H	3-COOCH 3
3-148	H	4-COOCH 3
3-149	H	2,3-COOCH 3
3-150	H	2,4-COOCH 3
3-151	H	2,5-COOCH 3
3-152	H	2,6-COOCH 3
3-153	H	3,4-COOCH 3

3-154	H	3,5-COOCH 3
3-155	H	2-NHCH 3
3-156	H	3-NHCH 3
3-157	H	4-NHCH 3
3-158	H	2-N(CH 3 ) 2
3-159	H	3-N(CH 3 ) 2
3-160	H	4-N(CH 3 ) 2
3-161	H	2-SCH 3
3-162	H	3-SCH 3
3-163	H	4-SCH 3
3-164	H	2-OCHF 2
3-165	H	3-OCHF 2
3-166	H	4-OCHF 2

Table 4:

Compound number	R 1	R 2
4-1	CH 3	H
4-2	CH 3	2-F
4-3	CH 3	3-F
4-4	CH 3	4-F
4-5	CH 3	2,3-F
4-6	CH 3	2,4-F
4-7	CH 3	2,5-F
4-8	CH 3	2,6-F
4-9	CH 3	3,4-F
4-10	CH 3	3,5-F
4-11	CH 3	2,3,4-F
4-12	CH 3	2,3,5-F
4-13	CH 3	2,3,6-F
4-14	CH 3	2,4,5-F
4-15	CH 3	2,4,6-F
4-16	CH 3	3,4,5-F
4-17	CH 3	2-Cl
4-18	CH 3	3-Cl
4-19	CH 3	4-Cl
4-20	CH 3	2,3-Cl
4-21	CH 3	2,4-Cl
4-22	CH 3	2,5-Cl
4-23	CH 3	2,6-Cl
4-24	CH 3	3,4-Cl
4-25	CH 3	3,5-Cl
4-26	CH 3	2,3,4-Cl
4-27	CH 3	2,3,5-Cl

4-28	CH 3	2,3,6-Cl
4-29	CH 3	2,4,5-Cl
4-30	CH 3	2,4,6-Cl
4-31	CH 3	3,4,5-Cl
4-32	CH 3	2-Br
4-33	CH 3	3-Br
4-34	CH 3	4-Br
4-35	CH 3	2,3-Br
4-36	CH 3	2,4-Br
4-37	CH 3	2,5-Br
4-38	CH 3	2,6-Br
4-39	CH 3	3,4-Br
4-40	CH 3	3,5-Br
4-41	CH 3	2,3,4-Br
4-42	CH 3	2,3,5-Br
4-43	CH 3	2,3,6-Br
4-44	CH 3	2,4,5-Br
4-45	CH 3	2,4,6-Br
4-46	CH 3	3,4,5-Br
4-47	CH 3	2-I
4-48	CH 3	3-I
4-49	CH 3	4-I
4-50	CH 3	2,3-I
4-51	CH 3	2,4-I
4-52	CH 3	2,5-I
4-53	CH 3	2,6-I
4-54	CH 3	3,4-I
4-55	CH 3	3,5-I
4-56	CH 3	2,3,4-I
4-57	CH 3	2,3,5-I
4-58	CH 3	2,3,6-I
4-59	CH 3	2,4,5-I
4-60	CH 3	2,4,6-I
4-61	CH 3	3,4,5-I
4-62	CH 3	2-CH 3
4-63	CH 3	3-CH 3
4-64	CH 3	4-CH 3
4-65	CH 3	2,3-CH 3
4-66	CH 3	2,4-CH 3
4-67	CH 3	2,5-CH 3
4-68	CH 3	2,6-CH 3
4-69	CH 3	3,4-CH 3
4-70	CH 3	3,5-CH 3

4-71	CH 3	2,3,4-CH 3
4-72	CH 3	2,3,5-CH 3
4-73	CH 3	2,3,6-CH 3
4-74	CH 3	2,4,5-CH 3
4-75	CH 3	2,4,6-CH 3
4-76	CH 3	3,4,5-CH 3
4-77	CH 3	2-OCH 3
4-78	CH 3	3-OCH 3
4-79	CH 3	4-OCH 3
4-80	CH 3	2,3-OCH 3
4-81	CH 3	2,4-OCH 3
4-82	CH 3	2,5-OCH 3
4-83	CH 3	2,6-OCH 3
4-84	CH 3	3,4-OCH 3
4-85	CH 3	3,5-OCH 3
4-86	CH 3	2,3,4-OCH 3
4-87	CH 3	2,3,5-OCH 3
4-88	CH 3	2,3,6-OCH 3
4-89	CH 3	2,4,5-OCH 3
4-90	CH 3	2,4,6-OCH 3
4-91	CH 3	3,4,5-OCH 3
4-92	CH 3	2-CN
4-93	CH 3	3-CN
4-94	CH 3	4-CN
4-95	CH 3	2,3-CN
4-96	CH 3	2,4-CN
4-97	CH 3	2,5-CN
4-98	CH 3	2,6-CN
4-99	CH 3	3,4-CN
4-100	CH 3	3,5-CN
4-101	CH 3	2-NO 2
4-102	CH 3	3-NO 2
4-103	CH 3	4-NO 2
4-104	CH 3	2,3-NO 2
4-105	CH 3	2,4-NO 2
4-106	CH 3	2,5-NO 2
4-107	CH 3	2,6-NO 2
4-108	CH 3	3,4-NO 2
4-109	CH 3	3,5-NO 2
4-110	CH 3	2-OH
4-111	CH 3	3-OH
4-112	CH 3	4-OH
4-113	CH 3	2,3-OH

4-114	CH 3	2,4-OH
4-115	CH 3	2,5-OH
4-116	CH 3	2,6-OH
4-117	CH 3	3,4-OH
4-118	CH 3	3,5-OH
4-119	CH 3	2-CF 3
4-120	CH 3	3-CF 3
4-121	CH 3	4-CF 3
4-122	CH 3	2,3-CF 3
4-123	CH 3	2,4-CF 3
4-124	CH 3	2,5-CF 3
4-125	CH 3	2,6-CF 3
4-126	CH 3	3,4-CF 3
4-127	CH 3	3,5-CF 3
4-128	CH 3	2-OCF 3
4-129	CH 3	3-OCF 3
4-130	CH 3	4-OCF 3
4-131	CH 3	2,3-OCF 3
4-132	CH 3	2,4-OCF 3
4-133	CH 3	2,5-OCF 3
4-134	CH 3	2,6-OCF 3
4-135	CH 3	3,4-OCF 3
4-136	CH 3	3,5-OCF 3
4-137	CH 3	2-OCOCH 3
4-138	CH 3	3-OCOCH 3
4-139	CH 3	4-OCOCH 3
4-140	CH 3	2,3-OCOCH 3
4-141	CH 3	2,4-OCOCH 3
4-142	CH 3	2,5-OCOCH 3
4-143	CH 3	2,6-OCOCH 3
4-144	CH 3	3,4-OCOCH 3
4-145	CH 3	3,5-OCOCH 3
4-146	CH 3	2-COOCH 3
4-147	CH 3	3-COOCH 3
4-148	CH 3	4-COOCH 3
4-149	CH 3	2,3-COOCH 3
4-150	CH 3	2,4-COOCH 3
4-151	CH 3	2,5-COOCH 3
4-152	CH 3	2,6-COOCH 3
4-153	CH 3	3,4-COOCH 3
4-154	CH 3	3,5-COOCH 3
4-155	CH 3	2-NHCH 3
4-156	CH 3	3-NHCH 3

4-157	CH 3	4-NHCH 3
4-158	CH 3	2-N(CH 3 ) 2
4-159	CH 3	3-N(CH 3 ) 2
4-160	CH 3	4-N(CH 3 ) 2
4-161	CH 3	2-SCH 3
4-162	CH 3	3-SCH 3
4-163	CH 3	4-SCH 3
4-164	CH 3	2-OCHF 2
4-165	CH 3	3-OCHF 2
4-166	CH 3	4-OCHF 2

table 5:

Compound number	R 1	R 2
5-1	CH 2 CH 3	H
5-2	CH 2 CH 3	2-F
5-3	CH 2 CH 3	3-F
5-4	CH 2 CH 3	4-F
5-5	CH 2 CH 3	2,3-F
5-6	CH 2 CH 3	2,4-F
5-7	CH 2 CH 3	2,5-F
5-8	CH 2 CH 3	2,6-F
5-9	CH 2 CH 3	3,4-F
5-10	CH 2 CH 3	3,5-F
5-11	CH 2 CH 3	2,3,4-F
5-12	CH 2 CH 3	2,3,5-F
5-13	CH 2 CH 3	2,3,6-F
5-14	CH 2 CH 3	2,4,5-F
5-15	CH 2 CH 3	2,4,6-F
5-16	CH 2 CH 3	3,4,5-F
5-17	CH 2 CH 3	2-Cl
5-18	CH 2 CH 3	3-Cl
5-19	CH 2 CH 3	4-Cl
5-20	CH 2 CH 3	2,3-Cl
5-21	CH 2 CH 3	2,4-Cl
5-22	CH 2 CH 3	2,5-Cl
5-23	CH 2 CH 3	2,6-Cl
5-24	CH 2 CH 3	3,4-Cl
5-25	CH 2 CH 3	3,5-Cl
5-26	CH 2 CH 3	2,3,4-Cl
5-27	CH 2 CH 3	2,3,5-Cl
5-28	CH 2 CH 3	2,3,6-Cl
5-29	CH 2 CH 3	2,4,5-Cl
5-30	CH 2 CH 3	2,4,6-Cl

5-31	CH 2 CH 3	3,4,5-Cl
5-32	CH 2 CH 3	2-Br
5-33	CH 2 CH 3	3-Br
5-34	CH 2 CH 3	4-Br
5-35	CH 2 CH 3	2,3-Br
5-36	CH 2 CH 3	2,4-Br
5-37	CH 2 CH 3	2,5-Br
5-38	CH 2 CH 3	2,6-Br
5-39	CH 2 CH 3	3,4-Br
5-40	CH 2 CH 3	3,5-Br
5-41	CH 2 CH 3	2,3,4-Br
5-42	CH 2 CH 3	2,3,5-Br
5-43	CH 2 CH 3	2,3,6-Br
5-44	CH 2 CH 3	2,4,5-Br
5-45	CH 2 CH 3	2,4,6-Br
5-46	CH 2 CH 3	3,4,5-Br
5-47	CH 2 CH 3	2-I
5-48	CH 2 CH 3	3-I
5-49	CH 2 CH 3	4-I
5-50	CH 2 CH 3	2,3-I
5-51	CH 2 CH 3	2,4-I
5-52	CH 2 CH 3	2,5-I
5-53	CH 2 CH 3	2,6-I
5-54	CH 2 CH 3	3,4-I
5-55	CH 2 CH 3	3,5-I
5-56	CH 2 CH 3	2,3,4-I
5-57	CH 2 CH 3	2,3,5-I
5-58	CH 2 CH 3	2,3,6-I
5-59	CH 2 CH 3	2,4,5-I
5-60	CH 2 CH 3	2,4,6-I
5-61	CH 2 CH 3	3,4,5-I
5-62	CH 2 CH 3	2-CH 3
5-63	CH 2 CH 3	3-CH 3
5-64	CH 2 CH 3	4-CH 3
5-65	CH 2 CH 3	2,3-CH 3
5-66	CH 2 CH 3	2,4-CH 3
5-67	CH 2 CH 3	2,5-CH 3
5-68	CH 2 CH 3	2,6-CH 3
5-69	CH 2 CH 3	3,4-CH 3
5-70	CH 2 CH 3	3,5-CH 3
5-71	CH 2 CH 3	2,3,4-CH 3
5-72	CH 2 CH 3	2,3,5-CH 3
5-73	CH 2 CH 3	2,3,6-CH 3

5-74	CH 2 CH 3	2,4,5-CH 3
5-75	CH 2 CH 3	2,4,6-CH 3
5-76	CH 2 CH 3	3,4,5-CH 3
5-77	CH 2 CH 3	2-OCH 3
5-78	CH 2 CH 3	3-OCH 3
5-79	CH 2 CH 3	4-OCH 3
5-80	CH 2 CH 3	2,3-OCH 3
5-81	CH 2 CH 3	2,4-OCH 3
5-82	CH 2 CH 3	2,5-OCH 3
5-83	CH 2 CH 3	2,6-OCH 3
5-84	CH 2 CH 3	3,4-OCH 3
5-85	CH 2 CH 3	3,5-OCH 3
5-86	CH 2 CH 3	2,3,4-OCH 3
5-87	CH 2 CH 3	2,3,5-OCH 3
5-88	CH 2 CH 3	2,3,6-OCH 3
5-89	CH 2 CH 3	2,4,5-OCH 3
5-90	CH 2 CH 3	2,4,6-OCH 3
5-91	CH 2 CH 3	3,4,5-OCH 3
5-92	CH 2 CH 3	2-CN
5-93	CH 2 CH 3	3-CN
5-94	CH 2 CH 3	4-CN
5-95	CH 2 CH 3	2,3-CN
5-96	CH 2 CH 3	2,4-CN
5-97	CH 2 CH 3	2,5-CN
5-98	CH 2 CH 3	2,6-CN
5-99	CH 2 CH 3	3,4-CN
5-100	CH 2 CH 3	3,5-CN
5-101	CH 2 CH 3	2-NO 2
5-102	CH 2 CH 3	3-NO 2
5-103	CH 2 CH 3	4-NO 2
5-104	CH 2 CH 3	2,3-NO 2
5-105	CH 2 CH 3	2,4-NO 2
5-106	CH 2 CH 3	2,5-NO 2
5-107	CH 2 CH 3	2,6-NO 2
5-108	CH 2 CH 3	3,4-NO 2
5-109	CH 2 CH 3	3,5-NO 2
5-110	CH 2 CH 3	2-OH
5-111	CH 2 CH 3	3-OH
5-112	CH 2 CH 3	4-OH
5-113	CH 2 CH 3	2,3-OH
5-114	CH 2 CH 3	2,4-OH
5-115	CH 2 CH 3	2,5-OH
5-116	CH 2 CH 3	2,6-OH

5-117	CH 2 CH 3	3,4-OH
5-118	CH 2 CH 3	3,5-OH
5-119	CH 2 CH 3	2-CF 3
5-120	CH 2 CH 3	3-CF 3
5-121	CH 2 CH 3	4-CF 3
5-122	CH 2 CH 3	2,3-CF 3
5-123	CH 2 CH 3	2,4-CF 3
5-124	CH 2 CH 3	2,5-CF 3
5-125	CH 2 CH 3	2,6-CF 3
5-126	CH 2 CH 3	3,4-CF 3
5-127	CH 2 CH 3	3,5-CF 3
5-128	CH 2 CH 3	2-OCF 3
5-129	CH 2 CH 3	3-OCF 3
5-130	CH 2 CH 3	4-OCF 3
5-131	CH 2 CH 3	2,3-OCF 3
5-132	CH 2 CH 3	2,4-OCF 3
5-133	CH 2 CH 3	2,5-OCF 3
5-134	CH 2 CH 3	2,6-OCF 3
5-135	CH 2 CH 3	3,4-OCF 3
5-136	CH 2 CH 3	3,5-OCF 3
5-137	CH 2 CH 3	2-OCOCH 3
5-138	CH 2 CH 3	3-OCOCH 3
5-139	CH 2 CH 3	4-OCOCH 3
5-140	CH 2 CH 3	2,3-OCOCH 3
5-141	CH 2 CH 3	2,4-OCOCH 3
5-142	CH 2 CH 3	2,5-OCOCH 3
5-143	CH 2 CH 3	2,6-OCOCH 3
5-144	CH 2 CH 3	3,4-OCOCH 3
5-145	CH 2 CH 3	3,5-OCOCH 3
5-146	CH 2 CH 3	2-COOCH 3
5-147	CH 2 CH 3	3-COOCH 3
5-148	CH 2 CH 3	4-COOCH 3
5-149	CH 2 CH 3	2,3-COOCH 3
5-150	CH 2 CH 3	2,4-COOCH 3
5-151	CH 2 CH 3	2,5-COOCH 3
5-152	CH 2 CH 3	2,6-COOCH 3
5-153	CH 2 CH 3	3,4-COOCH 3
5-154	CH 2 CH 3	3,5-COOCH 3
5-155	CH 2 CH 3	2-NHCH 3
5-156	CH 2 CH 3	3-NHCH 3
5-157	CH 2 CH 3	4-NHCH 3
5-158	CH 2 CH 3	2-N(CH 3 ) 2
5-159	CH 2 CH 3	3-N(CH 3 ) 2

5-160	CH 2 CH 3	4-N(CH 3 ) 2
5-161	CH 2 CH 3	2-SCH 3
5-162	CH 2 CH 3	3-SCH 3
5-163	CH 2 CH 3	4-SCH 3
5-164	CH 2 CH 3	2-OCHF 2
5-165	CH 2 CH 3	3-OCHF 2
5-166	CH 2 CH 3	4-OCHF 2

The present invention also provides a bactericide, which comprises an S-substituted-thiosemicarbazone structure compound represented by formula I or a salt thereof.

According to an embodiment of the present invention, the bactericide also includes agriculturally acceptable auxiliary agents, and optionally agents with other functions related to agricultural production.

According to an embodiment of the present invention, the bactericide may also include other active ingredients having bactericidal activity in addition to the S-substituted-thiosemicarbazone structure compound represented by formula I or a salt thereof.

The present invention also provides the application of the S-substituted-thiosemicarbazone structure compound represented by formula I or its salt as an active component in the preparation of a fungicide.

According to an embodiment of the present invention, the weight percentage of the active component is 0.1-99%.

The fungicide of the present invention can be used to prevent and control diseases including but not limited to the following diseases: Oomycetes, such as downy mildew (cucumber downy mildew, rape downy mildew, soybean downy mildew, beet downy mildew, sugarcane downy mildew) , Tobacco downy mildew, pea downy mildew, loofah downy mildew, wax gourd downy mildew, melon downy mildew, cabbage downy mildew, spinach downy mildew, turnip downy mildew, grape downy mildew, onion downy mildew Disease), white rust fungus (canola white rust, cabbage-like white rust), damping-off (cole damping-off, tobacco damping-off, tomato damping-off, pepper damping-off, eggplant damping-off, cucumber damping-off , Cotton seedling damping-off), cotton rot (pepper cotton rot, loofah cotton rot, wax gourd cotton rot), blight (broad bean blight, cucumber blight, pumpkin blight, winter melon blight, watermelon blight, melon blight, pepper blight) , Leek blight, garlic blight, cotton blight), late blight (potato late blight, tomato late blight), etc.; imperfect fungal diseases, such as blight (sweet potato blight, cotton blight, sesame blight, castor blight, Tomato wilt, bean wilt, cucumber wilt, loofah wilt, pumpkin wilt, wax gourd wilt, watermelon wilt, melon wilt, pepper wilt, broad bean wilt, rape wilt, soybean wilt), root Rot (pepper root rot, eggplant root rot, bean root rot, cucumber root rot, bitter gourd root rot, cotton black root rot, broad bean root rot), blast (cotton seedling wilt, Sesame blight, pepper blight, cucumber blight, cabbage blight), anthracnose (sorghum anthracnose, cotton anthracnose, kenaf anthracnose, jute anthracnose, flax anthracnose, tobacco anthracnose, mulberry Anthrax, pepper anthracnose, eggplant anthracnose, bean anthracnose, cucumber anthracnose, bitter gourd anthracnose, zucchini anthracnose, wax gourd anthracnose, watermelon anthracnose, melon anthracnose, litchi anthracnose, red bean anthracnose), Verticillium wilt Diseases (cotton verticillium wilt, sunflower verticillium wilt, tomato verticillium wilt, pepper verticillium wilt, eggplant verticillium wilt), scab (summer squash scab, wax gourd scab, melon scab), gray mold Diseases (cotton boll gray mold, kenaf gray mold, tomato gray mold, pepper gray mold, bean gray mold, celery gray mold, spinach gray mold, kiwi gray mold), brown spot (cotton brown Brown spot, jute brown spot, beet brown spot, peanut brown spot, pepper brown spot, wax gourd brown spot, soybean brown spot, sunflower brown spot, pea brown spot, broad bean brown spot), black Spot disease (flax pseudo black spot, rape black spot, sesame black spot, sunflower black spot, castor bean black spot, tomato black spot, pepper black spot, eggplant black spot, kidney bean black spot, Cucumber black spot, celery black spot, carrot black spot, carrot black spot, apple black spot, peanut black spot), spot blight (tomato spot blight, pepper spot blight, celery spot blight) , Early blight (tomato early blight, pepper early blight, eggplant early blight, potato early blight, celery early blight), ring disease (soybean ring disease, sesame ring disease, bean ring disease, apple ring disease), leaf Blight (sesame leaf blight, sunflower leaf blight, watermelon leaf blight, melon leaf blight), stem base rot (tomato stem base rot, vegetable Bean stem basal rot), and others (corn round spot, kenaf waist break, rice blast, chestnut black sheath disease, sugarcane eye spot, cotton boll aspergillosis, peanut crown rot, soybean stem blight, soybean black Spot disease, muskmelon large spot disease, peanut net spot disease, tea red leaf spot, pepper white star disease, wax gourd leaf spot, celery black rot, spinach heart rot, kenaf leaf mold, kenaf spot, jute Stem leaf spot, soybean purple spot, sesame leaf spot, castor gray spot, brown leaf spot, eggplant brown round star disease, bean erythema, bitter gourd white spot, watermelon spot, jute rot, sunflower root rot Disease, bean charcoal rot, soybean target spot disease, eggplant coryneform leaf spot, cucumber target spot disease, tomato leaf mold, eggplant leaf mold, broad bean red spot, etc.); basidiomycete diseases, such as rust (wheat Stripe rust, wheat stem rust, wheat leaf rust, flower rust, sunflower rust, sugarcane rust, leek rust, onion rust, chestnut rust, soybean rust), smut (corn head smut, corn smut, sorghum silk Head smut, sorghum smut, sorghum hard smut, sorghum smut, chestnut smut, sugarcane smut, bean rust) and others (such as wheat sheath blight, rice sheath blight, etc. ) Etc.; Ascomycete diseases, such as powdery mildew (wheat powdery mildew, rape powdery mildew, sesame powdery mildew, sunflower powdery mildew, beet powdery mildew, eggplant powdery mildew, pea powdery mildew, loofah powdery mildew, pumpkin powdery mildew, zucchini powdery mildew) , Wax gourd powdery mildew, melon powdery mildew, grape powdery mildew, broad bean powdery mildew), sclerotinia (flax sclerotinia, rape sclerotinia, soybean sclerotinia, peanut sclerotinia, tobacco sclerotinia, pepper sclerotium Disease, eggplant sclerotium, bean sclerotia, pea sclerotia, cucumber sclerotium, bitter melon sclerotia, wax gourd sclerotia, watermelon sclerotium, celery sclerotia), black spot (apple black star) Disease, pear scab), Gibberella wheat, Pythium fruit, Tobacco target spot, Cucumber Botrytis and so on.

The present invention also provides a preparation method of the S-substituted-thiosemicarbazone structure compound represented by formula I, which comprises the following steps:

1) The compound represented by formula A is reacted with thiosemicarbazide to obtain the compound represented by formula B;

2) Step 1) The compound represented by formula B is reacted with the compound represented by formula C to obtain the compound represented by formula I;

Wherein, X is selected from bromine or chlorine;

R ¹ and R ² are as defined above.

According to an embodiment of the present invention, in step 1), the compound represented by formula A is reacted with thiosemicarbazide under acidic conditions to obtain intermediate B.

According to an embodiment of the present invention, in step 1), the acid used to adjust the acidic conditions can be selected from, for example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, trifluoroacetic acid, acetic acid, methanesulfonic acid, toluenesulfonic acid, p-toluenesulfonic acid, etc., But preferred is concentrated hydrochloric acid.

According to an embodiment of the present invention, in step 1), the reaction is carried out in a suitable solvent, which can be selected from, for example, tetrahydrofuran, 1,4-dioxane, acetonitrile, toluene, xylene, benzene, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, acetone or methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, etc., Anhydrous ethanol is preferred.

According to an embodiment of the present invention, in step 1), the reaction temperature can be from 0°C to the boiling temperature of the solvent, for example, it can be 40-100°C, such as 40-80°C.

According to an embodiment of the present invention, in step 1), the reaction time is 0.5 to 30 hours, for example, 3 to 10 hours.

According to an embodiment of the present invention, in step 2), the compound represented by formula B reacts with the compound represented by formula C under acidic conditions to obtain the compound represented by formula I.

According to an embodiment of the present invention, in step 2), the acid used to adjust the acidic conditions can be selected from, for example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, trifluoroacetic acid, acetic acid, methanesulfonic acid, toluenesulfonic acid, p-toluenesulfonic acid, etc., Concentrated hydrochloric acid is preferred.

According to an embodiment of the present invention, in step 2), the reaction is carried out in a suitable solvent, which can be selected from, for example, tetrahydrofuran, 1,4-dioxane, acetonitrile, toluene, xylene, benzene, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, acetone or methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, etc., Anhydrous ethanol is preferred.

According to an embodiment of the present invention, in step 2), the reaction temperature is 0°C to the boiling point temperature of the solvent, for example, it can be 40-100°C, such as 40-80°C.

According to an embodiment of the present invention, in step 2), the reaction time is 0.5 hours to 30 hours, for example, 2 to 5 hours.

Beneficial effect

The S-substituted-thiosemicarbazone compound represented by formula I of the present invention has an excellent control effect on common agricultural pathogens, and is superior to the positive drug azoxystrobin in in vitro and in vivo tests, and can replace or supplement the existing market The potential of fungicides.

Terms and definitions

Unless otherwise defined, all scientific and technological terms herein have the same meanings as commonly understood by those skilled in the art to which the subject of the claims belongs.

"C ₁ -C ₁₂ "means having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms. "C ₃ -C ₁₂ "means having 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms. "C ₂ -C ₁₂ "means having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms. In the same way, "C ₁ -C ₆ "and "C ₃ -C ₆ " represent the corresponding number of carbon atoms.

Halogen: refers to fluorine, chlorine, bromine or iodine.

Alkyl: straight or branched chain alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl or tert-butyl.

Cycloalkyl: A substituted or unsubstituted heteroatom-containing cyclic alkyl group, such as cyclopropyl, cyclopentyl or cyclohexyl. Its substituents include methyl, halogen and the like.

Heterocycloalkyl: substituted or unsubstituted cyclic alkyl containing one or more N, O, S heteroatoms, such as tetrahydrofuranyl, cyclopentapiperidinyl. Its substituents include methyl, halogen and the like.

Halogenated alkyl groups: straight or branched chain alkyl groups. The hydrogen atoms on these alkyl groups can be partially or fully replaced by halogen atoms, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, dichloromethane, Fluoromethyl, trifluoromethyl, etc.

Alkoxy: straight or branched chain alkyl, connected to the structure via an oxygen atom bond.

Halogenated alkoxy groups: straight-chain or branched-chain alkoxy groups. The hydrogen atoms on these alkoxy groups may be partially or completely replaced by halogen atoms. For example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy and the like.

Alkoxyalkyl: The alkoxy group is attached to the structure via the alkyl group. Such as -CH ₂ OCH ₃ , -CH ₂ OCH ₂ CH ₃ .

Halogenated alkoxyalkyl: The hydrogen atoms on the alkyl group of the alkoxyalkyl group may be partially or completely replaced by halogen atoms. Such as -CH ₂ OCH ₂ CH ₂ Cl.

Alkylthio: straight or branched chain alkyl, connected to the structure via a sulfur atom bond.

Halogenated alkylthio: linear or branched alkylthio. The hydrogen atoms on these alkyl groups may be partially or completely replaced by halogen atoms. For example, chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio and the like.

Alkenyl: straight or branched chain alkenes, such as vinyl, 1-propenyl, 2-propenyl and the different butenyl, pentenyl and hexenyl isomers. Alkenyl also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl.

Alkynyl: linear or branched alkynes, such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. Alkynyl groups also include groups composed of multiple triple bonds, such as 2,5-hexadiynyl.

Alkenyloxy: straight or branched chain alkenes, connected to the structure via an oxygen atom bond.

Halogenated alkenyloxy groups: straight or branched chain alkenyloxy groups. The hydrogen atoms on these alkenyloxy groups may be partially or completely replaced by halogen atoms.

Alkynoxy: straight-chain or branched alkynes, connected to the structure via an oxygen atom bond.

Halogenated alkynyloxy groups: straight or branched chain alkynyloxy groups. The hydrogen atoms on these alkynyloxy groups may be partially or completely replaced by halogen atoms.

Alkylcarbonyl: A straight or branched chain alkyl group is connected to the structure via a carbonyl group (-CO-), such as an acetyl group.

Halogenated alkylcarbonyl: straight or branched chain alkylcarbonyl, the hydrogen atoms on the alkyl group can be partially or completely replaced by halogen atoms, such as trifluoroacetyl.

Alkoxycarbonyl: The alkoxy is attached to the structure via the carbonyl group. Such as -COOCH ₃ , -COOCH ₂ CH ₃ .

Halogenated alkoxycarbonyl: The hydrogen atoms on the alkyl group of the alkoxycarbonyl group can be partially or completely replaced by halogen atoms, such as -COOCH ₂ CF ₃ , -COOCH ₂ CH ₂ Cl and so on.

Alkylsulfonyl: A straight or branched chain alkyl group is _{connected to the structure via a sulfonyl group (-SO 2} -), such as a methylsulfonyl group.

Halogenated alkylsulfonyl: linear or branched alkylsulfonyl, the hydrogen atoms on the alkyl group can be partially or completely replaced by halogen atoms.

Alkylsulfonyloxy: alkyl-SO ₂ -O-.

Halogenated alkylsulfonyloxy group: The hydrogen atoms on the alkyl group of the alkylsulfonyloxy group may be partially or completely replaced by halogen atoms, such as CF ₃ -SO ₂ -O.

Alkoxycarbonylalkyl: alkoxycarbonyl-alkyl-, for example CH ₃ OCOCH ₂ -.

Halogenated alkoxycarbonylalkyl: The hydrogen atoms on the alkyl group of the alkoxycarbonylalkyl group may be partially or completely replaced by halogen atoms, such as CF ₃ CH ₂ OCOCH ₂ -.

Alkoxycarbonyloxy: alkoxycarbonyl- _{oxy-, for example CH 3} OCOO-.

Halogenated alkoxycarbonyloxy: The hydrogen atoms on the alkyl group of the alkoxycarbonyloxy group may be partially or completely replaced by halogen atoms, such as CF ₃ OCOO-.

Alkylthiocarbonylalkyl: alkylthiocarbonyl-alkyl-, for example CH ₃ SCOCH ₂ -.

Halogenated alkylthiocarbonylalkyl: The hydrogen atoms on the alkyl group of the alkylthiocarbonylalkyl group can be partially or completely replaced by halogen atoms, such as CF ₃ CH ₂ SCOCH ₂ -.

Alkoxyalkoxy: such as CH ₃ OCH ₂ O- and the like.

Halogenated alkoxy alkoxy: The hydrogen atoms on the alkoxy group can be partially or completely replaced by halogen atoms, such as CF ₃ OCH ₂ O-.

Alkylthioalkyl: alkyl-S-alkyl-, for example CH ₃ SCH ₂ -.

Halogenated alkylthioalkyl: The hydrogen atoms on the alkyl group of the alkylthioalkyl group can be partially or completely replaced by halogen atoms, such as ClCH ₂ CH ₂ SCH ₂ -, CF ₃ CH ₂ SCH ₂ -and so on.

Description of the drawings

Figure 1 shows the hydrogen NMR spectrum of compound 3-19.

Detailed ways

The technical solution of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following examples are only illustrative and explaining the present invention, and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the foregoing contents of the present invention are covered by the scope of the present invention.

Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.

Example 1 Preparation of compound 3-19

Combine (E)-2-(2-(bromomethyl)phenyl)-3-methoxymethyl acrylate 2.8g (10mmol), thiosemicarbazide 0.9g (10mmol), 25ml of absolute ethanol and three drops Concentrated hydrochloric acid was put into a 100mL three-necked flask, and the temperature was raised to 80°C and maintained for 5 hours. Thin layer chromatography (TLC) tracks the progress of the reaction. After the material is completely converted, it cools down, and a yellow solid precipitates out. It was filtered and dried to obtain 1.6 g of methyl (E)-2-(2-(((((E)-carbamoylhydrazino)thio)methyl)phenyl)-3-methoxyacrylate as a yellow solid.

1.6g (5.3mmol), 4- 0.85 g (6 mmol) of chlorobenzaldehyde, 25 mL of absolute ethanol and three drops of concentrated hydrochloric acid were put into a 100 mL three-necked flask, and the temperature was raised to 80° C. and maintained for 3 hours. Thin layer chromatography (TLC) to track the progress of the reaction. After the material conversion is completed, it is cooled and purified by column chromatography to obtain 0.62 g of a light yellow solid. The NMR map is shown in Figure 1.

Compound 3-19:

¹ H NMR (600MHz, DMSO- _d6 ) δ 9.83 (s, 2H), 8.60 (s, 1H), 8.00 (d, J = 8.4 Hz, 2H), 7.70 (s, 1H), 7.57 (d, J =8.1Hz,3H),7.35-7.30(m,2H),7.12-7.07(m,1H),4.55(s,2H),3.87(s,3H),3.63(s,3H).

Example 2 In vitro protective activity test

The plate method (hyphae growth rate method) was used. First, the test compound sample (the positive control drug used is azoxystrobin) is dissolved in a suitable solvent (the type of solvent is acetone, methanol, DMF, etc., and is selected according to its ability to dissolve the sample) to prepare the desired The concentration of the solution to be tested. In an ultra-clean working environment, use a pipette to add the measured solution to the melted PDA (at 45-50°C) (potato dextrose medium), and shake it quickly to prepare a drug-containing medium of the corresponding concentration , Pour it into 3 petri dishes while it is hot, and set aside after cooling. Inoculate bacterial clumps with a diameter of 5 mm and culture at 25±1°C for 7 days (full growth of colonies in the blank control is the standard). Measure the diameter of the colony (cross method), and calculate the inhibition rate according to the following formula:

_{The test results showed that the EC 50} values (mg/L) of compound 3-19 against rice grain wither, apple ring pattern, red bean anthracnose, cucumber sclerotia, g. tritici, and cotton verticillium wilt were all lower than 5ppm. _{The positive control drug azoxystrobin has EC 50} values (mg/L) greater than 10 ppm for rice sheath blight, apple ring pattern, red bean anthracnose, cucumber sclerotia, g. tritici, and cotton verticillium wilt.

_{In addition, the EC 50} values (mg/L) of compound 3-19 against Pythium acarpa, tobacco target spot and cucumber Botrytis cinerea are all lower than 35ppm, while the control positive drug azoxystrobin has an effect on Pythium acarpa, tobacco target spot and _{The EC 50} values (mg/L) of Cucumber Botrytis cinerea are higher than 35ppm.

The specific test results are shown in Table 1 below.

Table 1 Experimental results of bactericidal activity

_{In addition, the EC 50} values of other compounds of the present invention on rice grain wither, apple ring pattern, red bean anthracnose, cucumber wilt, cucumber sclerotia, Pythium fruit, tobacco target spot, Gibberella wheat, Verticillium wilt and Cucumber Botrytis cinerea (mg/L) is preferably less than 50 ppm, more preferably less than 20 ppm, and still more preferably less than 5 ppm.

Example 3 Determination of in vivo protective activity:

The determination method is as follows: the in vivo pot determination method is used, that is, the sample of the test compound (the positive control drug used is azoxystrobin) uses a small amount of solvent (the type of solvent is acetone, methanol, DMF, etc.), and depends on its ability to dissolve the sample. Optionally, the volume ratio of the solvent volume to the spray volume is equal to or less than 0.05) to dissolve, dilute with water containing 0.1% Tween 80, and prepare the required concentration of the test solution. On a crop sprayer, spray the test solution on the diseased host plant (the host plant rice is a standard potted seedling cultivated in the greenhouse), and then the disease is inoculated after 24 hours. According to the characteristics of the disease, the diseased plants that require temperature control and moisturizing culture are inoculated and cultured in an artificial climate room. After the disease is infected, they are moved to the greenhouse for cultivation, and the diseased plants that do not need moisturizing culture are directly inoculated and cultivated in the greenhouse. After the control is fully onset (usually one week), the compound's disease prevention effect will be evaluated.

Calculation method of efficacy:

At a dose of 100 ppm, the control effect of compound 3-19 on rice sheath blight is more than 80%. The control effect of the positive drug azoxystrobin is less than 70%.

The control effect of other compounds of the present invention is more than 50%, preferably more than 70%, and more preferably more than 80%.

It can be seen from the above activity test results that the S-substituted-thiosemicarbazone compound represented by the general formula I has an excellent control effect on common agricultural pathogens, and is superior to the positive drug azoxystrobin in in vitro and in vivo tests, and has an alternative Or supplement the potential of existing fungicides on the market.

In the foregoing, the embodiments of the present invention have been described. However, the present invention is not limited to the above-mentioned embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The S-substituted-thiosemicarbazone structure compound represented by formula I and its salt,

   

   in,

   R ^{1 is} selected from H, C ₁ -C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, C ₁ -C ₁₂ alkoxycarbonyl, C ₁ -C ₁₂ alkoxy C ₁ -C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkoxy C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkyl sulfide C ₁ -C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkylthio C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxycarbonyl C ₁ -C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkoxycarbonyl C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkylthiocarbonyl C ₁ -C ₁₂ alkyl group, halo C ₁ -C ₁₂ alkylthiocarbonyl C ₁ -C ₁₂ alkyl group;

   R ^{2 is} selected from H, halogen, hydroxyl, amino, nitro, cyano, carboxy, C ₁ -C ₁₂ alkyl, halo C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, halo C ₁ -C ₁₂ alkoxy, C ₃ -C ₁₂ cycloalkyl, -OC ₃ -C ₁₂ cycloalkyl, C ₁ -C ₁₂ alkylamino, halogenated C ₁ -C ₁₂ alkylamino, two (C _1- C ₁₂ alkyl)amino, -NHC ₃ -C ₁₂ cycloalkyl, halogenated di(C ₁ -C ₁₂ alkyl)amino, di(C ₁ -C ₁₂ alkyl)aminocarbonyl, C ₁ -C ₁₂ alkylthio, -SC ₃ -C ₁₂ cycloalkyl, halogenated C ₁ -C ₁₂ alkylthio, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ alkynyl, C ₂ -C ₁₂ alkenyloxy , Halogenated C ₂ -C ₁₂ alkenyloxy, C ₂ -C ₁₂ alkynyloxy, halogenated C ₂ -C ₁₂ alkynyloxy, C ₁ -C ₁₂ alkylsulfonyl, halogenated C ₁ -C ₁₂ alkane Sulfonyl, C ₁ -C ₁₂ alkylcarbonyl, -OCOC ₁ -C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkylcarbonyl, C ₁ -C ₁₂ alkoxycarbonyl, halogenated C ₁ -C ₁₂ Alkoxycarbonyl, C ₁ -C ₁₂ alkoxy C ₁ -C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkoxy C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkylthio C _1- C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkylthio C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxycarbonyl C ₁ -C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkoxy Carbonyl C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkylthiocarbonyl C ₁ -C ₁₂ alkyl, halogenated C ₁ -C ₁₂ alkylthiocarbonyl C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ Alkylcarbonyloxy, halogenated C ₁ -C ₁₂ alkylcarbonyloxy, C ₁ -C ₁₂ alkoxycarbonyloxy, halogenated C ₁ -C ₁₂ alkoxycarbonyloxy, C ₁ -C ₁₂ Alkylsulfonyloxy, halogenated C ₁ -C ₁₂ alkylsulfonyloxy, C ₁ -C ₁₂ alkoxy C ₁ -C ₁₂ alkoxy or halogenated C ₁ -C ₁₂ alkoxy C ₁ -C ₁₂ alkoxy;

   The number of R ² substituents is 1-5, and when it is 1-5, each R ² substituent is the same or different.
2. The compound according to claim 1, wherein R ^{1 is} selected from H, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylthio C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkylthio C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxycarbonyl C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkoxycarbonyl C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylthiocarbonyl C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ Alkylthiocarbonyl C ₁ -C ₆ alkyl;

   R ^{2 is} selected from H, halogen, hydroxyl, amino, nitro, cyano, carboxy, C ₁ -C ₆ alkyl, halo C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halo C ₁ -C ₆ alkoxy, C ₃ -C ₆ cycloalkyl, -OC ₃ -C ₆ cycloalkyl, C ₁ -C ₆ alkylamino, halogenated C ₁ -C ₆ alkylamino, two (C _1- C ₆ alkyl) amino, -NHC ₃ -C ₆ cycloalkyl, halogenated bis (C ₁ -C ₆ alkyl) amino, bis (C ₁ -C ₆ alkyl) amino carbonyl, C ₁ -C ₆ alkylthio, -SC ₃ -C ₆ cycloalkyl, halogenated C ₁ -C ₆ alkylthio, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₂ -C ₆ alkenyloxy , Halogenated C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ alkynyloxy, halogenated C ₂ -C ₆ alkynyloxy, C ₁ -C ₆ alkylsulfonyl, halogenated C ₁ -C ₆ alkane Sulfonyl, C ₁ -C ₆ alkylcarbonyl, -OCOC ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl, halogenated C ₁ -C ₆ Alkoxycarbonyl, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkoxy C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylthio C _1- C ₆ alkyl, halogenated C ₁ -C ₆ alkylthio C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxycarbonyl C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkoxy Carbonyl C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylthiocarbonyl C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkylthiocarbonyl C ₁ -C ₆ alkyl, C ₁ -C ₆ Alkylcarbonyloxy, halogenated C ₁ -C ₆ alkylcarbonyloxy, C ₁ -C ₆ alkoxycarbonyloxy, halogenated C ₁ -C ₆ alkoxycarbonyloxy, C ₁ -C ₆ Alkylsulfonyloxy, halogenated C ₁ -C ₆ alkylsulfonyloxy, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkoxy or halogenated C ₁ -C ₆ alkoxy C ₁ -C ₆ alkoxy;

   The number of R ² substituents is 1-4, and when it is 1-4, each R ² substituent is the same or different.
3. The compound according to claim 2, wherein R ^{1 is} selected from H, C ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₁ -C ₃ alkoxycarbonyl, C ₁ -C ₃ alkoxy C ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ alkoxy C ₁ -C ₃ alkyl, C ₁ -C ₃ alkylthio C ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ alkylthio C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxycarbonyl C _1- C ₃ alkyl, halogenated C ₁ -C ₃ alkoxycarbonyl C ₁ -C ₃ alkyl, C ₁ -C ₃ alkylthiocarbonyl C ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ Alkylthiocarbonyl C ₁ -C ₃ alkyl;

   R ^{2 is} selected from H, halogen, hydroxyl, amino, nitro, cyano, carboxy, C ₁ -C ₃ alkyl, halo C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy, halo C ₁ -C ₃ alkoxy, C ₃ -C ₆ cycloalkyl, -OC ₃ -C ₄ cycloalkyl, C ₁ -C ₃ alkylamino, halogenated C ₁ -C ₃ alkylamino, two (C _1- C ₃ alkyl)amino, -NHC ₃ -C ₄ cycloalkyl, halogenated di(C ₁ -C ₃ alkyl)amino, di(C ₁ -C ₃ alkyl)aminocarbonyl, C ₁ -C ₃ alkylthio, -SC ₃ -C ₄ cycloalkyl, halogenated C ₁ -C ₃ alkylthio, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₂ -C ₄ alkenyloxy , Halogenated C ₂ -C ₄ alkenyloxy, C ₂ -C ₄ alkynyloxy, halogenated C ₂ -C ₄ alkynyloxy, C ₁ -C ₃ alkylsulfonyl, halogenated C ₁ -C ₃ alkane Sulfonyl, C ₁ -C ₃ alkylcarbonyl, -OCOC ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ alkylcarbonyl, C ₁ -C ₃ alkoxycarbonyl, halogenated C ₁ -C ₃ Alkoxycarbonyl, C ₁ -C ₃ alkoxy C ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ alkoxy C ₁ -C ₃ alkyl, C ₁ -C ₃ alkylthio C _1- C ₃ alkyl, halogenated C ₁ -C ₃ alkylthio C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxycarbonyl C ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ alkoxy Carbonyl C ₁ -C ₃ alkyl, C ₁ -C ₃ alkylthiocarbonyl C ₁ -C ₃ alkyl, halogenated C ₁ -C ₃ alkylthiocarbonyl C ₁ -C ₃ alkyl, C ₁ -C ₃ Alkylcarbonyloxy, halogenated C ₁ -C ₃ alkylcarbonyloxy, C ₁ -C ₃ alkoxycarbonyloxy, halogenated C ₁ -C ₃ alkoxycarbonyloxy, C ₁ -C ₃ Alkylsulfonyloxy, halogenated C ₁ -C ₃ alkylsulfonyloxy, C ₁ -C ₃ alkoxy C ₁ -C ₃ alkoxy or halogenated C ₁ -C ₃ alkoxy C ₁ -C ₃ alkoxy;

   The number of R ² substituents is 1, 2, 3, or 4, and when it is 1 to 4, each R ² substituent is the same or different.
4. The compound of claim 3, wherein R ^{1 is} selected from the following groups:

   

   R ^{2 is} selected from the following groups:

   

   

   in,

   

   Where is the connection site.
5. The compound of claim 4, wherein R ^{1 is} selected from the following groups: H, methyl;

   R ^{2 is} selected from the following groups:

   H, 2-nitro, 3-nitro, 4-nitro, 2-methyl, 3-methyl, 4-methyl, 2-methoxy, 3-methoxy, 4-methoxy, 2-fluoro, 3-fluoro, 4-fluoro, 2-chloro, 3-chloro, 4-chloro, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2-trifluoromethyl Oxy, 3-trifluoromethoxy, 4-trifluoromethoxy, 4chloro-2-fluoro, 3,4-dimethyl, 2,4-difluoro, 3,4,5-trifluoro, 2-fluoro-5-trifluoromethyl, 2,4,6 trifluoro, 2,4,5-trifluoro, 2,3,4-trifluoro, 3,4-difluoro, 3-trifluoromethyl -4-fluoro, 4-hydroxy, 2,4-dihydroxy, 3,4-dimethoxy, 4-fluoro-3-cyano, 2,4-dimethoxy, 3-hydroxy, 3-hydroxy -4-methoxy, 3,4-dimethoxy, 3-methyl-4-fluoro.
6. The compound of claim 5, wherein:

   When R ¹ is H, R ^{2 is} selected from the following groups:

   H, 2-nitro, 3-nitro, 4-nitro, 2-methyl, 3-methyl, 4-methyl, 2-methoxy, 3-methoxy, 4-methoxy, 2-fluoro, 3-fluoro, 4-fluoro, 2-chloro, 3-chloro, 4-chloro, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2-trifluoromethyl Oxy, 3-trifluoromethoxy, 4-trifluoromethoxy, 2,4-difluoro, 3,4,5-trifluoro, 2-fluoro-5-trifluoromethyl, 2,4, 6-trifluoro, 2,4,5-trifluoro, 2,3,4-trifluoro, 3,4-difluoro, 3-trifluoromethyl-4-fluoro, 4-hydroxy, 2,4-di Hydroxyl, 3,4-dimethoxy, 4-fluoro-3-cyano, 2,4-dimethoxy, 3-hydroxy, 3-hydroxy-4-methoxy, 3,4-dimethoxy base;

   Preferably, when R ¹ is a methyl group, R ^{2 is} selected from the following groups:

   H, 4-nitro, 3-methyl, 3-trifluoromethyl, 4chloro-2-fluoro, 3,4-dimethyl, 2,4-difluoro, 4-hydroxy, 2,4-di Hydroxy, 2-chloro, 3-methyl-4-fluoro, 4-methyl, 3-chloro, 2-fluoro, 4-methyl, 4-chloro.
7. A bactericide, characterized by comprising the S-substituted-thiosemicarbazone structure compound of formula I according to any one of claims 1 to 6, or a salt thereof.
8. The fungicide according to claim 7, characterized in that it further comprises an agriculturally acceptable auxiliary agent, and optionally an agent with other functions related to agricultural production.
9. The use of the S-substituted-thiosemicarbazone structure compound represented by any one of claims 1 to 6 as an active component in the preparation of a bactericide.
10. The application according to claim 9, wherein the weight percentage of the active component is 0.1-99%.

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