WO2020169046A1 - Use of 1,1-dicyanohydrazone compound as agricultural bactericide - Google Patents

Abstract

Disclosed in the present invention is the use of a 1,1-dicyanohydrazone compound as shown in general formula (I) as an agricultural bactericide. The definition of each substituent in the formula is described in the description. The compound of general formula (I) has an excellent bactericidal activity and can be used to control various bacterial diseases for plants.

Description

Application of 1,1-dicyanohydrazone compound as agricultural bactericide Technical field

The present invention belongs to the field of agricultural bactericides, and specifically relates to the application of a 1,1-dicyanohydrazone compound as an agricultural bactericide.

Background technique

Bacterial diseases have become the second most common disease in my country’s agricultural production after fungal diseases. According to incomplete statistics, the area of bacterial diseases currently occurring in my country is 120 million mu, and the market capacity of bacterial disease prevention and control exceeds 20. 100 million yuan. At present, in agricultural production, agents for the prevention and control of bacterial diseases mainly include relatively large amounts of copper preparations (including organic or inorganic copper preparations) and antibiotic products; among them, copper preparations have low control effect and a large amount of heavy metals are sprayed into the environment. Pollution of soil, water and food has caused environmental and food safety concerns. On the other hand, the large-scale use of antibiotics may cause human pathogens to become resistant to medical antibiotics. There are only a small number of other varieties that can be used for agricultural bacterial treatment. In actual production, they are limited by resistance and control effect, and the promotion area is small. Therefore, it is very necessary and urgent to research and develop new, high-efficiency, low-toxicity, and environment-friendly bacterial disease control agents.

In the prior art, the application of 1,1-dicyanohydrazone compounds as shown in the present invention as agricultural bactericides has not been reported.

Summary of the invention

The purpose of the present invention is to provide a 1,1-dicyanohydrazone compound represented by general formula I for controlling plant bacterial diseases in agriculture or forestry.

The technical scheme of the present invention is as follows:

The application of a 1,1-dicyanohydrazone compound as an agricultural bactericide, wherein the structure of the 1,1-dicyanohydrazone compound is shown in general formula I:

Where:

W is selected from one of the groups represented by W ₁ -W ₃ :

among them:

X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ , X ₈ , X ₉ , X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ , X ₁₄ , X ₁₅ , X ₁₆ , X ₁₇ , X ₁₈ and X ₁₉ are each independently selected from hydrogen, halogen, cyano, nitro, hydroxy, mercapto, amino, carboxy, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C _1- C ₆ alkoxy, halogenated C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, halogenated C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylamino, C ₁ -C ₆ Dialkylamino, C ₁ -C ₆ alkylcarbonyl or C ₁ -C ₆ alkoxycarbonyl;

G is selected from hydrogen, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, cyano C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylcarbonyl, C ₃ -C ₆ cycloalkyl Carbonyl or C ₁ -C ₆ alkoxycarbonyl;

Or a tautomer of the compound of formula I;

Or the salt of the compound of formula I.

When the compound of general formula I is used as an agricultural bactericide, further preferred compounds are:

W is selected from one of the groups represented by W ₁ -W ₃ ;

X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ , X ₈ , X ₉ , X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ , X ₁₄ , X ₁₅ , X ₁₆ , X ₁₇ , X ₁₈ and X ₁₉ are each independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, mercapto, amino, carboxy, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C _1- C ₄ alkoxy, halogenated C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, halogenated C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylamino, C ₁ -C ₄ Dialkylamino, C ₁ -C ₄ alkylcarbonyl or C ₁ -C ₄ alkoxycarbonyl;

G is selected from hydrogen, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, cyano C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylcarbonyl, C ₃ -C ₆ cycloalkyl Carbonyl or C ₁ -C ₄ alkoxycarbonyl;

Or a tautomer of the compound of formula I;

Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.

When the compound of general formula I is used as an agricultural bactericide, further preferred compounds are:

W is selected from one of the groups represented by W ₁ -W ₃ ;

X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ , X ₈ , X ₉ , X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ , X ₁₄ , X ₁₅ , X ₁₆ , X ₁₇ , X ₁₈ and X ₁₉ are each independently selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, hydroxyl, mercapto, amino, carboxy, methyl, ethyl, n-propyl, isopropyl, n-butyl , Isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoro Methyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, methoxy, ethoxy, n-propoxy, isopropoxy, difluoromethoxy, three Fluoromethoxy, methylthio, ethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, methylamino, ethylamino, N,N-dimethylamino, methoxycarbonyl Or ethoxycarbonyl;

G is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, Monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, cyanomethyl , Acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl;

Or a tautomer of the compound of formula I;

Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.

When the compound of formula I is used as an agricultural bactericide, further preferred compounds are:

W is selected from one of the groups represented by W ₁ -W ₃ ;

X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ , X ₈ , X ₉ , X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ , X ₁₄ , X ₁₅ , X ₁₆ , X ₁₇ , X ₁₈ and X ₁₉ are each independently selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, carboxy, methyl, ethyl, tert-butyl, trifluoromethyl, methoxy, trifluoromethoxy Group, methoxycarbonyl or ethoxycarbonyl;

G is selected from hydrogen, methyl, ethyl, acetyl, cyclopropylformyl, methoxycarbonyl or ethoxycarbonyl;

Or a tautomer of the compound of formula I;

Or a salt formed by a compound of formula I with hydrochloric acid, hydrobromic acid, sulfuric acid or phosphoric acid.

In the definitions of compounds of the general formula given above, the terms used in pooling generally represent the following substituents:

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

Alkyl: straight or branched chain alkyl, such as methyl, ethyl, n-propyl, isopropyl or different butyl, pentyl or hexyl isomers.

Halogenated alkyl groups: straight or branched chain alkyl groups. The hydrogen atoms on these alkyl groups can be partially or completely replaced by halogens, such as monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, and dichloromethyl. Bromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, etc.

Cyanoalkyl: straight-chain or branched-chain alkyl. The hydrogen atoms on these alkyl groups can be partially or completely replaced by cyano groups, such as cyanomethyl (CNCH ₂ -), cyanoethyl (CNCH ₂ CH ₂ -) ), CNCH ₂ CH ₂ CH ₂ -, CNCH ₂ CH ₂ CH ₂ CH ₂ -etc.

Alkoxy: straight or branched chain alkyl, connected to the structure via oxygen atom bond, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, etc. .

Halogenated alkoxy groups: straight or branched chain alkoxy groups, the hydrogen atoms on these alkoxy groups can be partially or completely replaced by halogen, such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluorine Methoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, 2,2,2-trifluoroethoxy, etc.

Alkylthio: straight or branched chain alkyl, connected to the structure via a sulfur atom bond, such as methylthio, ethylthio and the like.

Halogenated alkylthio: linear or branched alkylthio, the hydrogen atoms on these alkylthio groups can be partially or completely replaced by halogen, such as difluoromethylthio, trifluoromethylthio, 2,2,2- Trifluoroethylthio and so on.

Alkylamino: straight or branched chain alkyl, connected to the structure via a nitrogen atom bond, such as methylamino, ethylamino, n-propylamino, isopropylamino or isomeric butylamine.

Dialkylamino: Two identical or different linear or branched alkyl groups are connected to the structure via a nitrogen atom bond, such as N,N-dimethylamino, N-methyl-N-ethylamino, etc.

Alkylcarbonyl: The alkyl group is connected to the structure via the carbonyl group, such as acetyl (CH ₃ CO-), n-propionyl (CH ₃ CH ₂ CO-) and so on.

Cycloalkylcarbonyl: A cycloalkyl is attached to the structure via a carbonyl group, such as cyclopropylformyl.

Alkoxycarbonyl: alkyl-O-CO-, such as methoxycarbonyl (CH ₃ OCO-), ethoxycarbonyl (CH ₃ CH ₂ OCO-), n-propoxycarbonyl (CH ₃ CH ₂ CH ₂ OCO-), n-butoxycarbonyl (CH ₃ CH ₂ CH ₂ CH ₂ OCO-), etc.

In the general formula I shown in the present invention, when G is a hydrogen atom, the compound of general formula I has the following tautomers, and the compound of general formula I also includes, in this case, all tautomers.

Some of the compounds of general formula I of the present invention are shown in Tables 1 to 9, but the present invention is by no means limited to these compounds.

In the general formula I, when W=W ₁ , the general formula I can be represented by the general formula IW ₁ (for ease of description, the substituents X ₁ , X ₂ , X ₃ , X ₄ , and X _{5 of} W ₁ are represented by R, below with).

Table 1: In the general formula IW ₁ , when G=H, R is a different substituent. See Table 1, which represents compound numbers 1.1-1.354.

Table 1

Numbering	R	Numbering	R	Numbering	R
1.1	2-F	1.2	2-Cl	1.3	2-Br
1.4	3-F	1.5	3-Cl	1.6	3-Br
1.7	4-F	1.8	4-Cl	1.9	4-Br
1.10	2-I	1.11	2-CN	1.12	2-NO 2
1.13	3-I	1.14	3-CN	1.15	3-NO 2
1.16	4-I	1.17	4-CN	1.18	4-NO 2
1.19	2-CH 3	1.20	2-C 2 H 5	1.21	2-CH 2 CH 2 CH 3
1.22	3-CH 3	1.23	3-C 2 H 5	1.24	3-CH 2 CH 2 CH 3
1.25	4-CH 3	1.26	4-C 2 H 5	1.27	4-CH 2 CH 2 CH 3
1.28	2-CH(CH 3 ) 2	1.29	2-CH 2 CH 2 CH 2 CH 3	1.30	2-C(CH 3 ) 3
1.31	3-CH(CH 3 ) 2	1.32	3-CH 2 CH 2 CH 2 CH 3	1.33	3-C(CH 3 ) 3
1.34	4-CH(CH 3 ) 2	1.35	4-CH 2 CH 2 CH 2 CH 3	1.36	4-C(CH 3 ) 3
1.37	2-CF 3	1.38	2-CF(CF 3 ) 2	1.39	2-OCH 3
1.40	3-CF 3	1.41	3-CF(CF 3 ) 2	1.42	3-OCH 3
1.43	4-CF 3	1.44	4-CF(CF 3 ) 2	1.45	4-OCH 3
1.46	2-OC 2 H 5	1.47	2-OCF 3	1.48	2-OCHF 2
1.49	3-OC 2 H 5	1.50	3-OCF 3	1.51	3-OCHF 2
1.52	4-OC 2 H 5	1.53	4-OCF 3	1.54	4-OCHF 2
1.55	2-OCH 2 CF 3	1.56	2-SCH 3	1.57	2-SCF 3
1.58	3-OCH 2 CF 3	1.59	3-SCH 3	1.60	3-SCF 3
1.61	4-OCH 2 CF 3	1.62	4-SCH 3	1.63	4-SCF 3

1.64	2-OH	1.65	2-SH	1.66	2-NH 2
1.67	3-OH	1.68	3-SH	1.69	3-NH 2
1.70	4-OH	1.71	4-SH	1.72	4-NH 2
1.73	2-COOH	1.74	2-NHCH 3	1.75	2-NHCH 2 CH 3
1.76	3-COOH	1.77	3-NHCH 3	1.78	3-NHCH 2 CH 3
1.79	4-COOH	1.80	4-NHCH 3	1.81	4-NHCH 2 CH 3
1.82	2-N(CH 3 ) 2	1.83	2-N(CH 3 )(CH 2 CH 3 )	1.84	2-(O=C)CH 3
1.85	3-N(CH 3 ) 2	1.86	3-N(CH 3 )(CH 2 CH 3 )	1.87	3-(O=C)CH 3
1.88	4-N(CH 3 ) 2	1.89	4-N(CH 3 )(CH 2 CH 3 )	1.90	4-(O=C)CH 3
1.91	2-(O=C)OCH 3	1.92	3-(O=C)OCH 3	1.93	4-(O=C)OCH 3
1.94	2-(O=C)OCH 2 CH 3	1.95	3-(O=C)OCH 2 CH 3	1.96	4-(O=C)OCH 2 CH 3
1.97	2,3-2F	1.98	2,3-2Cl	1.99	2,3-2Br
1.100	2,4-2F	1.101	2,4-2Cl	1.102	2,4-2Br
1.103	2,5-2F	1.104	2,5-2Cl	1.105	2,5-2Br
1.106	2,6-2F	1.107	2,6-2Cl	1.108	2,6-2Br
1.109	3,4-2F	1.110	3,4-2Cl	1.111	3,4-2Br
1.112	3,5-2F	1.113	3,5-2Cl	1.114	3,5-2Br
1.115	2,3-2CN	1.116	2,3-2NO 2	1.117	2,3-2CH 3
1.118	2,4-2CN	1.119	2,4-2NO 2	1.120	2,4-2CH 3
1.121	2,5-2CN	1.122	2,5-2NO 2	1.123	2,5-2CH 3
1.124	2,6-2CN	1.125	2,6-2NO 2	1.126	2,6-2CH 3
1.127	3,4-2CN	1.128	3,4-2NO 2	1.129	3,4-2CH 3
1.130	3,5-2CN	1.131	3,5-2NO 2	1.132	3,5-2CH 3
1.133	2,3-2C 2 H 5	1.134	2,3-2(CH 2 ) 2 CH 3	1.135	2,3-2CH(CH 3 ) 2
1.136	2,4-2C 2 H 5	1.137	2,4-2(CH 2 ) 2 CH 3	1.138	2,4-2CH(CH 3 ) 2
1.139	2,5-2C 2 H 5	1.140	2,5-2(CH 2 ) 2 CH 3	1.141	2,5-2CH(CH 3 ) 2
1.142	2,6-2C 2 H 5	1.143	2,6-2(CH 2 ) 2 CH 3	1.144	2,6-2CH(CH 3 ) 2
1.145	3,4-2C 2 H 5	1.146	3,4-2(CH 2 ) 2 CH 3	1.147	3,4-2CH(CH 3 ) 2
1.148	3,5-2C 2 H 5	1.149	3,5-2(CH 2 ) 2 CH 3	1.150	3,5-2CH(CH 3 ) 2
1.151	2,3-2C(CH 3 ) 3	1.152	2,3-2CF 3	1.153	2,3-2OCH 3
1.154	2,4-2C(CH 3 ) 3	1.155	2,4-2CF 3	1.156	2,4-2OCH 3
1.157	2,5-2C(CH 3 ) 3	1.158	2,5-2CF 3	1.159	2,5-2OCH 3
1.160	2,6-2C(CH 3 ) 3	1.161	2,6-2CF 3	1.162	2,6-2OCH 3
1.163	3,4-2C(CH 3 ) 3	1.164	3,4-2CF 3	1.165	3,4-2OCH 3

1.166	3,5-2C(CH 3 ) 3	1.167	3,5-2CF 3	1.168	3,5-2OCH 3
1.169	2,3-2OCF 3	1.170	2,3-2SCH 3	1.171	2,3-2SCF 3
1.172	2,4-2OCF 3	1.173	2,4-2SCH 3	1.174	2,4-2SCF 3
1.175	2,5-2OCF 3	1.176	2,5-2SCH 3	1.177	2,5-2SCF 3
1.178	2,6-2OCF 3	1.179	2,6-2SCH 3	1.180	2,6-2SCF 3
1.181	3,4-2OCF 3	1.182	3,4-2SCH 3	1.183	3,4-2SCF 3
1.184	3,5-2OCF 3	1.185	3,5-2SCH 3	1.186	3,5-2SCF 3
1.187	2-F-4-Cl	1.188	2-F-4-Br	1.189	2-F-4-I
1.190	2-F-3-Cl	1.191	2-F-5-Cl	1.192	2-F-6-Cl
1.193	3-F-2-Cl	1.194	3-F-4-Cl	1.195	3-F-5-Cl
1.196	3-F-6-Cl	1.197	4-F-2-Cl	1.198	4-F-3-Cl
1.199	2-Cl-4-Br	1.200	2-Cl-4-I	1.201	3-Cl-4-I
1.202	4-Cl-2-Br	1.203	2-CN-3-F	1.204	3-Cl-4-Br
1.205	2-CN-4-Cl	1.206	2-CN-4-Br	1.207	2-CN-4-NO 2
1.208	4-CN-2-Cl	1.209	4-CN-2-CF 3	1.210	4-CN-2-NO 2
1.211	2-NO 2 -4-F	1.212	2-NO 2 -4-Cl	1.213	2-NO 2 -4-Br
1.214	2-NO 2 -4-OCH 3	1.215	2-NO 2 -4-OC 2 H 5	1.216	2-NO 2 -5-Cl
1.217	3-NO 2 -4-F	1.218	3-NO 2 -4-Cl	1.219	3-NO 2 -4-Br
1.220	4-NO 2 -2-Cl	1.221	4-NO 2 -2-OCH 3	1.222	5-NO 2 -2-F
1.223	5-NO 2 -2-Cl	1.224	5-NO 2 -2-Br	1.225	5-NO 2 -2-OCH 3
1.226	2-CH 3 -4-F	1.227	2-CH 3 -4-Cl	1.228	2-CH 3 -4-Br
1.229	2-CH 3 -4-I	1.230	2-CH 3 -4-NO 2	1.231	2-CH 3 -4-OCH 3
1.232	2-CH 3 -3-F	1.233	2-CH 3 -3-Cl	1.234	2-CH 3 -3-NO 2
1.235	2-CH 3 -5-F	1.236	2-CH 3 -5-Cl	1.237	2-CH 3 -5-Br
1.238	2-CH 3 -5-NO 2	1.239	2-CH 3 -6-Cl	1.240	2-CH 3 -6-C 2 H 5
1.241	2-CH 3 -6-NO 2	1.242	3-CH 3 -2-Cl	1.243	3-CH 3 -2-Br
1.244	3-CH 3 -4-Cl	1.245	3-CH 3 -4-Br	1.246	3-CH 3 -4-I
1.247	4-CH 3 -2-Cl	1.248	4-CH 3 -3-Cl	1.249	4-CH 3 -2-Br
1.250	4-CH 3 -3-Br	1.251	4-CH 3 -3-F	1.252	4-CH 3 -2-NO 2
1.253	4-CH 3 -3-NO 2	1.254	5-CH 3 -2-F	1.255	5-CH 3 -2-CN
1.256	5-CH 3 -2-OCH 3	1.257	4-C(CH 3 ) 3 -2-Cl	1.258	2-CF 3 -4-Cl
1.259	2-CF 3 -4-Br	1.260	2-CF 3 -4-NO 2	1.261	3-CF 3 -4-F
1.262	3-CF 3 -4-Cl	1.263	3-CF 3 -4-NO 2	1.264	4-CF 3 -2-Cl
1.265	4-CF 3 -2-Br	1.266	4-CF 3 -2-NO 2	1.267	5-CF 3 -2-Cl

1.268	5-CF 3 -2-Br	1.269	5-CF 3 -2-OCH 3	1.270	2-OCH 3 -5-Cl
1.271	4-OCH 3 -3-F	1.272	4-OCH 3 -3-Cl	1.273	2-OCF 3 -4-Cl
1.274	2-OCF 3 -4-Br	1.275	2-OCF 3 -4-CN	1.276	4-OCF 3 -2-Cl
1.277	4-OCF 3 -2-Br	1.278	4-OCF 3 -2-NO 2	1.279	2-SCH 3 -5-Cl
1.280	2,3,4-3F	1.281	2,3,4-3Cl	1.282	2,3,4-3Br
1.283	2,3,5-3F	1.284	2,3,5-3Cl	1.285	2,3,5-3Br
1.286	2,3,6-3F	1.287	2,3,6-3Cl	1.288	2,3,6-3Br
1.289	2,4,5-3F	1.290	2,4,5-3Cl	1.291	2,4,5-3Br
1.292	2,4,6-3F	1.293	2,4,6-3Cl	1.294	2,4,6-3Br
1.295	3,4,5-3F	1.296	3,4,5-3Cl	1.297	3,4,5-3Br
1.298	2,4,6-3CH 3	1.299	2,4,6-3C 2 H 5	1.300	2,4,6-3CH(CH 3 ) 2
1.301	2,4,6-3C(CH 3 ) 3	1.302	2,4,6-3CF 3	1.303	2,4,6-3NO 2
1.304	2,4,6-3OCH 3	1.305	3,4,5-3OCH 3	1.306	2,4,6-3OCF 3
1.307	2,4,6-3SCH 3	1.308	2,4,6-3SCF 3	1.309	2-F-4,6-2Br
1.310	2-F-4-Cl-6-Br	1.311	4-F-2,6-2Br	1.312	2,4-2F-6-Cl
1.313	2,3-2Cl-4-Br	1.314	2-CH 3 -4,6-2Br	1.315	3-CH 3 -2,6-2Cl
1.316	4-CH 3 -2,6-2Br	1.317	2,3-2CH 3 -6-NO 2	1.318	4,5-2CH 3 -2-NO 2
1.319	2,6-2CH 3 -4-C(CH 3 ) 3	1.320	2-CH 3 -4-NO 2 -6-Cl	1.321	2-CH 3 -4-NO 2 -6-Br
1.322	2-CH 3 -6-NO 2 -4-Cl	1.323	2-CH 3 -6-NO 2 -4-Br	1.324	5-CH 3 -4-F-6-Cl
1.325	5-CH 3 -2-OCH 3 -4-Cl	1.326	2-CF 3 -4,6-2Cl	1.327	2-CF 3 -4,6-2Br
1.328	4-CF 3 -2,6-2Cl	1.329	4-CF 3 -2,6-2Br	1.330	4-CF 3 -2-NO 2 -5-Cl
1.331	4-CF 3 -2-NO 2 -6-Cl	1.332	4-CF 3 -2-NO 2 -6-Br	1.333	4-CF 3 -2-Cl-6-Br
1.334	2-NO 2 -4,6-2Br	1.335	2-NO 2 -4-F-5-Cl	1.336	4-NO 2 -2,6-2Cl
1.337	4-NO 2 -2,6-2Br	1.338	4-NO 2 -2,5-2Cl	1.339	2,4-2NO 2 -6-Cl
1.340	2,4-2NO 2 -6-Br	1.341	2-CN-4,6-2Cl	1.342	2-CN-4,6-2Br
1.343	4-CN-2,6-2Cl	1.344	2-CN-4-NO 2 -6-Cl	1.345	2-CN-4-NO 2 -6-Br
1.346	2,5-2OCH 3 -4-NO 2	1.347	2,4-2OCH 3 -5-Cl	1.348	2,3,5,6-4F
1.349	4-F-3-Cl-2,6-2Br	1.350	6-NO 2 -2,3,4-3F	1.351	2,3,4,5,6-5F
1.352	2,3,4,5,6-5Cl	1.353	2,3,5,6-4F-4-CF 3	1.354	H

Table 2: In the general formula IW ₁ , when G=CH ₃ , the substituent R is consistent with Table 1, and the representative compound number is 2.1-2.354, corresponding to 1.1-1.354 of Table 1 in turn.

Table 3: In the general formula IW ₁ , when G=CH ₂ CH ₃ , the substituent R is consistent with Table 1, and the representative compound numbers are 3.1-3.354, corresponding to 1.1-1.354 in Table 1.

Table 4: In the general formula IW ₁ , when G = acetyl, the substituent R is consistent with Table 1, and the representative compound number is 4.1-4.354, corresponding to 1.1-1.354 of Table 1 in turn.

Table 5: In the general formula IW ₁ , when G=cyclopropylformyl, the substituent R is consistent with Table 1, and the representative compound number is 5.1-5.354, corresponding to 1.1-1.354 in Table 1 in turn.

Table 6: In the general formula IW ₁ , when G = methoxycarbonyl, the substituent R is consistent with Table 1, and the representative compound number is 6.1-6.354, corresponding to 1.1-1.354 of Table 1 in turn.

Table 7: In the general formula IW ₁ , when G=ethoxycarbonyl, the substituent R is consistent with Table 1, and the representative compound number is 7.1-7.354, corresponding to 1.1-1.354 in Table 1 in turn.

Formula I, where W = W _2, the general formula I may be represented by Formula IW _2.

Table 8: In the general formula IW ₂ , when X ₆ ＝X ₇ ＝X ₈ ＝X ₉ ＝X ₁₀ ＝X ₁₁ ＝X ₁₂ ＝H, G is a different substituent. See Table 8, representing the compound number 8.1- 8.12.

Table 8

Numbering	G	Numbering	G	Numbering	G
8.1	H	8.2	CH 3	8.3	CH 2 CH 3
8.4	CH 2 CH 2 CH 3	8.5	CH 2 CH 2 CH 2 CH 3	8.6	2,2,2-Trifluoroethyl
8.7	Acetyl	8.8	Cyclopropylformyl	8.9	Methoxycarbonyl
8.10	Ethoxycarbonyl	8.11	N-propoxycarbonyl	8.12	N-Butoxycarbonyl

In the general formula I, when W=W ₃ , the general formula I can be represented by the general formula IW ₃ .

Table 9: In the general formula IW ₃ , when X ₁₃ ＝X ₁₄ ＝X ₁₅ ＝X ₁₆ ＝X ₁₇ ＝X ₁₈ ＝X ₁₉ ＝H, G is a different substituent. See Table 9, which represents the compound number 9.1- 9.12.

Table 9

Numbering

G

Numbering

G

Numbering

G

9.1	H	9.2	CH 3	9.3	CH 2 CH 3
9.4	CH 2 CH 2 CH 3	9.5	CH 2 CH 2 CH 2 CH 3	9.6	2,2,2-Trifluoroethyl
9.7	Acetyl	9.8	Cyclopropylformyl	9.9	Methoxycarbonyl
9.10	Ethoxycarbonyl	9.11	N-propoxycarbonyl	9.12	N-Butoxycarbonyl

The physical and chemical properties of some compounds of the present invention are shown in Table 10, and their nuclear magnetic and mass spectrometry data are shown in Table 11.

Table 10

Note: "-" in Table 10 means no cas number.

Table 11

The compound of general formula I of the present invention can be prepared according to the following method (each group in the formula is defined as before unless otherwise specified):

In the compound of general formula I, when G is H, the compound is represented by general formula I-1, and when G is other substituents, the compound is represented by general formula I-2:

The compound of the general formula II can be prepared by the conventional diazotization reaction to produce the corresponding diazonium salt product, that is, the compound of the general formula III.

The compound of general formula III can be reacted with malononitrile in the presence of a suitable base in a suitable solvent at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours to prepare a compound of general formula I-1. Suitable base can be sodium acetate, potassium acetate, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide or tertiary Sodium butoxide and so on. Suitable solvent can be water, dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, methanol, ethanol, ethyl acetate, acetonitrile, dioxane, THF, DMF, DMSO or a mixture of the above solvents Solvent.

The compound of the general formula I-1 and the compound of the general formula G-LG can be reacted in a suitable solvent in an alkali-free or alkali-free environment at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours to obtain the general formula I -2 compounds. Suitable base can be sodium acetate, potassium acetate, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide or tertiary Sodium butoxide and so on. Suitable solvent can be water, dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, methanol, ethanol, ethyl acetate, acetonitrile, dioxane, THF, DMF, DMSO or a mixture of the above solvents Solvent. In the compound of the general formula G-LG, LG represents a leaving group, and a suitable leaving group can be halogen or other conventional nucleating groups, such as C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkyl sulfide Group, specifically, methoxy, ethoxy, methylthio or ethylthio.

The compound of general formula II, the compound of general formula G-LG and other raw materials and reagents are usually commercially available, and they can also be made by conventional methods.

The compounds of the present invention can also be prepared according to the methods disclosed in US3755598A, US3660462A, US3202698, US3157569, US3062635, JP07206800A, WO9735863A1, US4115104A, JP48087020A, JP48087019A, US3213124, US3135736 or European Journal of Biochemistry, 33(2), 247-52; 1973, etc. , Or refer to other known methods.

The compound represented by the general formula I of the present invention is used to control plant bacterial diseases, and can be used to prevent and control a variety of plant bacterial diseases, such as fruit spot (such as melon fruit spot, etc.), leaf spot (such as tomato bacteria) Leaf spot disease, etc.), bacterial wilt (such as tomato bacterial wilt, potato bacterial wilt, etc.), bacterial blight, canker disease (such as citrus canker, kiwi fruit canker, etc.), soft rot (such as soft Chinese cabbage) Rot, etc.), bacterial angular leaf spot (such as cucumber bacterial angular leaf spot, etc.), bacterial leaf streak (such as rice bacterial leaf spot, etc.), leaf blight, bacterial leaf blight (such as rice white leaf Blight, etc.), wildfire and bacterial scab.

detailed description

The following specific examples are used to further illustrate the present invention, but the present invention is by no means limited to these examples. (Unless otherwise noted, all raw materials used are commercially available)

Synthesis Example

According to the synthetic route described above, using different raw material compounds, the compounds represented by the general formula I of the present invention can be prepared separately, which are further specifically described as follows:

Example 1: Preparation of compound 1.19

Weigh 1.00 g (9.35 mmol) of o-toluidine and dissolve it in a mixed solution of 35 ml H ₂ O and 9 ml concentrated hydrochloric acid, and cool to 0-5°C; slowly add 0.67 g (9.71 mmol) of sodium nitrite to this solution 10 ml of ice water solution, during this process, maintain the reaction temperature at 0-5°C; after the addition is complete, continue to stir and react for 10 minutes under ice bath. The preparation of the diazonium salt solution is complete.

Weigh 22.15 g (270.12 mmol) of sodium acetate, add 100 ml of water, and cool to 0-5°C; add 0.92 g (13.94 mmol) of malononitrile; slowly add the above-prepared diazonium salt solution dropwise to this solution. During this process, the reaction temperature was maintained at 0-5°C; after the addition was completed, the reaction was continued with stirring for 30 minutes under an ice bath; after filtration and drying, the target compound was obtained as a yellow solid 1.22 g.

Example 2: Preparation of compound 1.110

Weigh 0.50 g (3.11 mmol) of 3,4-dichloroaniline and dissolve it in a mixed solution of 20 ml H ₂ O and 3 ml concentrated hydrochloric acid, and cool to 0-5°C; slowly add 0.22 g (3.19 mmol) to this solution. A 3 ml ice water solution of sodium nitrite maintains the reaction temperature at 0-5°C during this process; after the addition is complete, continue to stir and react for 10 minutes in an ice bath. The preparation of the diazonium salt solution is complete.

Weigh 7.80g (95.12mmol) of sodium acetate, add 35ml of water, and cool to 0-5℃; add 0.31g (4.70mmol) of malononitrile; slowly add dropwise the prepared diazonium salt solution to this solution while stirring During this process, maintain the reaction temperature at 0-5°C; after the addition is complete, continue to stir and react for 30 minutes in an ice bath. After filtration and drying, the target compound was obtained, 0.72 g of yellow solid.

Example 3: Preparation of compound 2.19

Weigh 0.35 g (1.90 mmol) of compound 1.19, 0.11 g (4.58 mmol) of sodium hydride, 0.54 g (3.80 mmol) of methyl iodide, add 15 ml of tetrahydrofuran, and stir the reaction at room temperature; after the reaction is monitored by TLC, quench the hydrogenation with an appropriate amount of water Sodium, add water and ethyl acetate for extraction, dry with anhydrous magnesium sulfate, filter, desolvate under reduced pressure, and column chromatography of the residue (eluent is ethyl acetate and petroleum ether, the volume ratio is 1:10～1:4 ) Purification to obtain the target compound, 0.23 g of gray solid.

Example 4: Preparation of compound 4.110

Weigh 0.50 g (2.10 mmol) of compound 1.110, 0.33 g (4.18 mmol) of pyridine, 0.20 g (2.56 mmol) of acetyl chloride, add 20 ml of dichloromethane, and stir the reaction at room temperature for 3 hours; after the reaction is monitored by TLC, remove under reduced pressure The residue was purified by column chromatography (eluent is ethyl acetate and petroleum ether, the volume ratio is 1:10 to 1:4) to obtain the target compound, 0.52 g of white solid.

Example 5: Preparation of compound 5.110

Weigh 0.35 g (1.47 mmol) of compound 1.110, 0.23 g (2.91 mmol) of pyridine, and 0.18 g (1.73 mmol) of cyclopropylformyl chloride, add 20 ml of dichloromethane, and stir the reaction at room temperature; after the reaction is monitored by TLC, reduce pressure The residue is purified by column chromatography (eluent is ethyl acetate and petroleum ether, the volume ratio is 1:10 to 1:4) to obtain the target compound, 0.32 g of white solid.

Example 6: Preparation of compound 7.110

Weigh 0.50 g (2.10 mmol) of compound 1.110, 0.10 g (4.17 mmol) of sodium hydride, 0.27 g (2.50 mmol) of ethyl chloroformate, and add 20 ml of tetrahydrofuran; increase the reaction temperature to 50°C, stir and react for 3 hours; TLC monitoring After the reaction is complete, quench the sodium hydride with an appropriate amount of water, add water and ethyl acetate for extraction, dry with anhydrous magnesium sulfate, filter, and remove the solvent under reduced pressure. The residue is column chromatographed (eluent is ethyl acetate and petroleum ether , The volume ratio is 1:10～1:4) to obtain the target compound, 0.55 g of gray solid.

Example 7: Preparation of compound 8.1

Weigh 0.80 g (5.59 mmol) of 1-naphthylamine and dissolve it in a mixed solution of 35 ml H ₂ O and 6 ml concentrated hydrochloric acid, and cool to 0-5°C; slowly add 0.41 g (5.94 mmol) sodium nitrite to this solution During this process, the reaction temperature was maintained at 0-5°C; after the addition was completed, the reaction was continued under ice bath with stirring for 10 minutes. The preparation of the diazonium salt solution is complete.

Weigh 13.76 g (167.80 mmol) of sodium acetate, add 60 ml of water, and cool to 0-5°C; add 0.55 g (8.33 mmol) of malononitrile; slowly add dropwise the diazonium salt solution prepared above to this solution, During this process, the reaction temperature was maintained at 0-5°C; after the addition was completed, the reaction was continued with stirring for 30 minutes under an ice bath; the target compound was obtained after filtration and drying, 0.78 g of a red solid.

Example 8: Preparation of Compound 8.2

Weigh 0.42g (1.91mmol) of compound 8.1, 0.12g (5.00mmol) of sodium hydride, 0.55g (3.87mmol) of methyl iodide, add 20ml of tetrahydrofuran, and stir the reaction at room temperature; after the reaction is monitored by TLC, quench the hydrogenation with an appropriate amount of water Sodium, add water and ethyl acetate for extraction, dry with anhydrous magnesium sulfate, filter, desolvate under reduced pressure, and column chromatography of the residue (eluent is ethyl acetate and petroleum ether, the volume ratio is 1:10～1:4 ) Purification to obtain the target compound, 0.25 g of white solid.

Example 9: Preparation of Compound 8.9

Weigh 0.32 g (1.45 mmol) of compound 8.1, 0.15 g (6.25 mmol) of sodium hydride, 0.16 g (1.70 mmol) of methyl chloroformate, and add 15 ml of tetrahydrofuran; increase the reaction temperature to 50°C, stir and react for 5 hours; TLC monitoring After the reaction is complete, quench the sodium hydride with an appropriate amount of water, add water and ethyl acetate for extraction, dry with anhydrous magnesium sulfate, filter, and remove the solvent under reduced pressure. The residue is column chromatographed (eluent is ethyl acetate and petroleum ether , The volume ratio is 1:10～1:4) Purify to obtain the target compound, 0.21 g of brown solid.

With reference to the above examples, other compounds of the general formula I of the present invention can be prepared.

Biological activity determination

Example 10: Determination of the control effect on plant bacterial diseases

The compound of the present invention has been used to determine the prevention effect of various plant bacterial diseases. For different bacterial diseases, the test procedure is as follows:

For melon fruit spot disease, dissolve the test compound with a small amount of N,N dimethylformamide and dilute with water to the required concentration. The pathogenic bacteria cultivated to the stable growth stage are mixed with the quantitative compound solution uniformly, the melon seeds that have been germinated are soaked in the mixture of the bacterial solution and the compound for half an hour, and then the seeds are sown in the earthworm soil culture cup and placed in the greenhouse Medium moisturizing culture, usually cultured for two weeks, after the control has fully developed the disease, the control effect will be investigated.

For Chinese cabbage soft rot, cut 2 cm square cabbage leaves and put them in a glass petri dish lined with double filter paper. The compound dissolved in N,N dimethylformamide and diluted with water to the required concentration is sprayed on the surface of the cabbage leaves. After drying the liquid on the surface of the cabbage leaves in a fume hood, acupuncture the surface of the cabbage leaves with an inoculation needle For the wound, 5 microliters of soft rot fungus of Chinese cabbage cultivated to a stable growth period is added to the wound for inoculation. Finally, the test materials were placed in an incubator for 48 hours in the dark, and the control effect was investigated after the control had fully developed disease.

Cucumber bacterial angular leaf spot, tomato bacterial leaf spot, rice bacterial leaf spot, rice bacterial leaf blight, dissolve the test compound with a small amount of N,N dimethylformamide, and dilute with water to the required concentration . The compound is sprayed on the surface of the plant test material, and after the surface drug solution is air-dried in a cool place, the pathogenic bacteria liquid cultured to a stable growth stage is sprayed on the surface of the plant test material, and then the plant test material is placed in a greenhouse for moisturizing culture. Usually cultured for about ten days, after the control is fully onset, the control effect investigation is carried out.

The test results are as follows:

At 600mg/L, compounds 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.17, 1.18, 1.19, 1.22, 1.25, 1.26, 1.36, 1.43, 1.45, 1.53, 1.79, 1.96, 1.98, 1.101, 1.104, 1.107, 1.110, 1.113, 1.129, 1.167, 1.267, 1.290, 1.293, 1.296, 1.298, 1.354, 2.19, 2.132, 2.167, 2.354, 4.110, 5.110, 6.101, 6.167, 7.98, 7.101, 7.110, 7.167, The control effect of 8.1, 8.2, 8.9, 8.10, 9.1 on melon fruit spot disease is 100%.

At 400 mg/L, compounds 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.17, 1.18, 1.19, 1.22, 1.25, 1.26, 1.36, 1.43, 1.45, 1.53, 1.79, 1.96, 1.98, 1.101, 1.104, 1.107, 1.110, 1.113, 1.129, 1.167, 1.267, 1.290, 1.293, 1.296, 1.298, 1.354, 2.19, 2.132, 2.167, 2.354, 4.110, 5.110, 6.101, 6.167, 7.98, 7.101, 7.110, 7.167, The control effects of 8.1, 8.2, 8.9, 8.10, 9.1 on cucumber bacterial angular leaf spot, rice bacterial leaf spot and rice bacterial leaf blight are all 100%.

At 400 mg/L, compounds 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.17, 1.18, 1.19, 1.22, 1.25, 1.26, 1.36, 1.43, 1.45, 1.53, 1.79, 1.96, 1.98, 1.101, 1.104, 1.107, 1.110, 1.113, 1.129, 1.167, 1.267, 1.290, 1.293, 1.296, 1.298, 1.354, 2.19, 2.132, 2.167, 2.354, 4.110, 5.110, 6.101, 6.167, 7.98, 7.101, 7.110, 7.167, The control effects of 8.1, 8.2, 8.9, 8.10, and 9.1 on soft rot of Chinese cabbage or bacterial leaf spot of tomato were all 100%.

Claims (6)

1. An application of 1,1-dicyanohydrazone compounds as agricultural bactericides, characterized in that the application of 1,1-dicyanohydrazone compounds as agricultural bactericides; wherein, 1,1-dicyanohydrazone The structure of base hydrazone compounds is shown in general formula I:

   

   Where:

   W is selected from one of the groups represented by W ₁ -W ₃ :

   

   among them:

   X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ , X ₈ , X ₉ , X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ , X ₁₄ , X ₁₅ , X ₁₆ , X ₁₇ , X ₁₈ and X ₁₉ are each independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, mercapto, amino, carboxy, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C _1- C ₆ alkoxy, halogenated C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, halogenated C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylamino, C ₁ -C ₆ Dialkylamino, C ₁ -C ₆ alkylcarbonyl or C ₁ -C ₆ alkoxycarbonyl;

   G is selected from hydrogen, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, cyano C ₁ -C ₆ alkyl, C ₁ -C ₆ alkylcarbonyl, C ₃ -C ₆ cycloalkyl Carbonyl or C ₁ -C ₆ alkoxycarbonyl;

   Or a tautomer of the compound of formula I;

   Or the salt of the compound of formula I.
2. The application according to claim 1, wherein the compound in the general formula I:

   W is selected from one of the groups represented by W ₁ -W ₃ ;

   X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ , X ₈ , X ₉ , X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ , X ₁₄ , X ₁₅ , X ₁₆ , X ₁₇ , X ₁₈ and X ₁₉ are each independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, mercapto, amino, carboxy, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, C _1- C ₄ alkoxy, halogenated C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, halogenated C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylamino, C ₁ -C ₄ Dialkylamino, C ₁ -C ₄ alkylcarbonyl or C ₁ -C ₄ alkoxycarbonyl;

   G is selected from hydrogen, C ₁ -C ₄ alkyl, halogenated C ₁ -C ₄ alkyl, cyano C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylcarbonyl, C ₃ -C ₆ cycloalkyl Carbonyl or C ₁ -C ₄ alkoxycarbonyl;

   Or a tautomer of the compound of formula I;

   Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
3. The application according to claim 2, characterized in that, in the general formula I of the compound,

   W is selected from one of the groups represented by W ₁ -W ₃ ;

   X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ , X ₈ , X ₉ , X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ , X ₁₄ , X ₁₅ , X ₁₆ , X ₁₇ , X ₁₈ and X ₁₉ are each independently selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, hydroxyl, mercapto, amino, carboxy, methyl, ethyl, n-propyl, isopropyl, n-butyl , Isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoro Methyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, methoxy, ethoxy, n-propoxy, isopropoxy, difluoromethoxy, three Fluoromethoxy, methylthio, ethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, methylamino, ethylamino, N,N-dimethylamino, methoxycarbonyl Or ethoxycarbonyl;

   G is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, Monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, cyanomethyl , Acetyl, n-propionyl, cyclopropylformyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or n-butoxycarbonyl;

   Or a tautomer of the compound of formula I;

   Or compound of general formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, apple Salts of acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.
4. The application according to claim 3, characterized in that, in the general formula I of the compound,

   W is selected from one of the groups represented by W ₁ -W ₃ ;

   X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , X ₇ , X ₈ , X ₉ , X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ , X ₁₄ , X ₁₅ , X ₁₆ , X ₁₇ , X ₁₈ and X ₁₉ are each independently selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, carboxy, methyl, ethyl, tert-butyl, trifluoromethyl, methoxy, trifluoromethoxy Group, methoxycarbonyl or ethoxycarbonyl;

   G is selected from hydrogen, methyl, ethyl, acetyl, cyclopropylformyl, methoxycarbonyl or ethoxycarbonyl;

   Or a tautomer of the compound of formula I;

   Or a salt formed by a compound of formula I with hydrochloric acid, hydrobromic acid, sulfuric acid or phosphoric acid.
5. The application of the 1,1-dicyanohydrazone compound as an agricultural bactericide according to any one of claims 1 to 4, characterized in that: the compound represented by the general formula I is used for controlling plant bacteria Application in STDs.
6. The application of 1,1-dicyanohydrazone compounds as agricultural bactericides according to claim 5, characterized in that: the plant bacterial diseases are fruit spot, leaf spot, bacterial wilt, bacterial Blight, ulcer, soft rot, bacterial angular leaf spot, bacterial leaf spot, leaf blight, bacterial leaf blight, wildfire or bacterial scab.