JPH045668B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application Field The present invention relates to anilinopyridazine derivatives and herbicides containing them. For more details, see the general formula () (In the formula, R represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, or a phenoxy group, n represents an integer of 1 to 5, and R ¹ represents a lower haloalkenyl group or a lower haloalkynyl group. group, and R ² represents a halogen atom.) Anilinopyridazine derivatives represented by
and a herbicide characterized by containing at least one of them as an active ingredient. Prior Art Many herbicides have been developed so far, but there has been a desire for one that is more efficient and safer for crops. Furthermore, in rice fields, weeds of the family Cyperaceae are difficult to control, and there has been a desire to develop herbicides effective against these weeds. Conventionally, it has been reported in Patent Publication Showa that anilinopyridazines, benzylaminopyridazines, or alkylaminopyridazines have herbicidal activity.
No. 41-19519, No. 47-43819, Chemical regulation of plants,
Volume 8, pages 10-20 (1973) and Journal of
Medicinal Chemistry, Vol. 6, p. 807 (1963), but practically sufficient herbicidal activity and selectivity have not been found. Namely, Patent Publication No. 19519 and 1973.
-43819, 3-chloro-6-substituted anilinopyridazine (

[Formula] Compound group A) has been described to have a physiological effect on plants, but the physiological effect is tested in a Petri dish. Generally, even if a physiological effect is expressed in a Petri dish test, it does not necessarily show the same effect as in a rice field.
The practicality is unknown. Furthermore, the test plants are barnyard grass and Japanese radish, and the effect on plants of the Cyperaceae family, which are harmful weeds, is not disclosed. Chemical Regulation of Plants, Vol. 8, pp. 10-20 (1973) describes compound group E.

Although the herbicidal activity of [Formula] is described, there is no mention of its effect on firefly and water cypress, which are harmful weeds in rice fields, and other herbicidal effects were also insufficient. Journal of Medicinal Chemistry, Volume 6, 807
(1963) describes compound group B.

[Formula] and compound C

[Formula] Only one item is listed. Regarding compound group B, there are descriptions regarding herbicidal activity against broad-leaved weeds or grass weeds, but there is no description regarding Cyperaceae plants.
Herbicidal activity is too low to be of practical use. Regarding Compound C, there is no description of herbicidal activity. Japanese Unexamined Patent Publication 1983-
Although Publication No. 77866 states that it is effective against the harmful weed Cyperaceae, its herbicidal activity was still insufficient for practical use. Purpose of the Invention Many herbicides have been developed so far, but it is difficult to control weeds of the Cyperaceae family in rice fields, and there has been a desire to develop a drug that can control weeds such as Japanese millet, including these weeds. . The object of the present invention is to provide a new compound that controls these weeds, namely, Japanese millet grass, firefly, Japanese cypress, and water cyperus, and is free from phytotoxicity, and a herbicide containing the same. Structure and operation of the invention The present inventors have conducted various studies on anilinopyridazine derivatives, and as a result, the general formula () (In the formula, R represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, or a phenoxy group, n represents an integer of 1 to 5, and R ¹ represents a lower haloalkenyl group or a lower haloalkynyl group. ( ^R2 represents a halogen atom) and compositions containing them have high herbicidal activity against Japanese millet, firefly, Japanese cyperus, and water cyperus, and have high herbicidal activity without phytotoxicity on rice. They found that it has selectivity and completed the present invention. Namely, Patent Publication No. 1951-19519, 1972
-43819, Chemical Regulation of Plants, Volume 8, Pages 10-20 (1973), Journal of Medicinal Chemistry, 6
In the exemplified compounds described in Compound Group B, etc. of Vol., p. 807 (1963), the pyridazine ring is substituted with a methyl group or a halogen atom, but the amino group is disclosed to be a secondary amine, not a tertiary amine. Journal of Medicinal Chemistry, Volume 6, 807
Compound C disclosed in Page (1963)

In [Formula], the pyridazine ring is not substituted with a methyl group. In Japanese Patent Application Laid-open No. 58-77866,

In the compound group of [Formula], R ¹ is a lower alkyl group, a lower alkenyl group, or a lower alkynyl group, the amine group is a tertiary amine, and the 4th position of the pyridazine ring is a methyl group. It is disclosed that grass activity is expressed. The present inventors have prepared an amine group in the compound of the present invention as represented by the general formula ().

[Formula] and R ¹ are substituted to form a tertiary amine, the pyridazine ring is substituted with an alkyl group and a halogen atom, and R ¹
By changing to a lower haloalkenyl group or a lower haloalkynyl group, the herbicidal activity against Cyperaceae weeds is further improved, and it also shows high herbicidal activity against Japanese millet, expanding the herbicidal spectrum and making it suitable for rice. The objective of the present invention has been achieved by realizing a surprising improvement in the effect that there is no phytotoxicity and even better selectivity. The compound of the present invention is a novel compound represented by the above general formula (), and the substituent R is a hydrogen atom, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a methyl group or an ethyl group. , n
-propyl group, i-propyl group, n-butyl group,
sec-butyl group, i-butyl group, tert-butyl group,
n-amyl group, i-amyl group, sec-amyl group,
Lower alkyl groups such as n-hersyl group or lower haloalkyl groups such as trifluoromethyl group, trichloromethyl group, difluorochloromethyl group, chloromethyl group, bromomethyl group, chloroethyl group, fluoroethyl group, bromoethyl group, or methoxy group, Examples include lower alkoxy groups such as ethoxy group, n-propoxy group, i-propoxy group, or phenoxy group, and R ¹ includes 1-chloro-2-propenyl group, 2-chloro-
2-propenyl group, 3-chloro-2-propenyl group, 2,3-dichloro-2-propenyl group, 1-
Bromo-2-propenyl group, 2-iodo-2-propenyl group, 3-iodo-2-propenyl group, 2
-bromo-2-propenyl group, 2-chloro-2-
Butenyl group, 2-bromo-2-butenyl group, 3-
Chloro-2-butenyl group, 3-bromo-2-butenyl group, 2,3-dichloro-2-butenyl group,
Lower haloalkenyl groups such as 2,4-dichloro-2-butenyl group, 3-chloro-2-propynyl group, 3-bromo-2-propynyl group, 3-iodo-2-propynyl group, 4-chloro-2 -butynyl group, 4-bromo-2-butynyl group, 4-iodo-2-butynyl group and other lower halorkynyl groups, but are not limited thereto. ^R2
Examples include halogen atoms such as fluorine atom, chlorine atom, bromine atom or iodine atom. The anilinopyridazine derivative of the present invention can be produced by the following method. i.e. general formula () (In the formula, X represents a halogen atom) and halopyridazines represented by the general formula () (In the formula, R represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, or a phenoxy group, n represents an integer of 1 to 5, and R ¹ represents a lower haloalkenyl group or a lower halo An alkynyl group) is reacted with an aniline represented by the formula () and a halopyridazine in an equivalent to 10 times equivalent ratio in an inert solvent or without a solvent to form the general formula (). (In the formula, R, R ¹ and n have the above meanings,
R ² represents a halogen atom. ) It is possible to produce an anilinopyridazine derivative represented by: Also, general formula () (In the formula, R represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, or a phenoxy group, n represents an integer of 1 to 5, and R ² represents a hagen atom.) Anilinopyridazines are reacted with a halide represented by ^the general formula R ¹ formula() An anilinopyridazine derivative represented by the formula (wherein R, R ¹ , R ² and n have the above-mentioned meanings) can be produced. Examples Next, the method for producing the compound of the present invention represented by the above general formula () will be explained using production examples. Production example N-(2-bromo-2-propenyl)-3
-Synthesis of chloro-6-anilino-4-methylpyridazine (compound 1) In a 300 ml reaction flask, 6-
Anilino-3-chloro-4-methylpyridazine
11.0 g of benzene, 100 ml of benzene, and 18.1 g of 2,3-dibromopropene-1 were charged. While thoroughly stirring at room temperature, 0.5 g of triethylbenzylammonium chloride and 75 ml of 25% aqueous sodium hydroxide solution were added. After stirring vigorously for 1 hour at room temperature, the benzene layer was separated, washed with water, dehydrated with anhydrous sodium sulfate, and the benzene was distilled off to obtain crude crystals. The crystals were recrystallized from benzene to obtain 6.95 g of N-(2-bromo-2-propenyl)-3-chloro-6-anilino-4-methylpyridazine. mp65
~67℃ Elemental analysis value (%) C; 49.63, H; 3.60, Br;
23.26 C1; 10.84, N; 12.34 Calculated value (%) C; 49.65, H; 3.87, Br; 23.60 C1; 10.46, N; 12.41 As a result of examining the NMR data of the compound obtained above, No broad singlet peak due to protons was observed, confirming that the raw material amino group was substituted with the bromopropenyl group. Furthermore, it was confirmed from the NMR data shown below that the bromine at the 3-position of 2,3-dibromopropene-1 was reacted with the raw material amino group. NMR chemical shift of bromopropenyl group NMR δ tms: 4.90 (2H, s) 5.64 (2H, s) (Assuming that the bromine at the 2-position of 2,3-dibromopropene-1 has reacted, the methyl group to which bromine is attached The chemical shifts of the two protons are further shifted to the lower magnetic field side.) Typical examples of compounds represented by the general formula () obtained by the above production method are listed below along with their physical properties.
Shown in the table. Compound number 2, 4, 5, 7, 8, 10, 11, 12,
The structures of Nos. 13 and 14 were determined in the same manner as in the above production example. In addition, compound No. 3 added 1,3-dichloropropene-
It is a product reacted with 1, and the obtained compound is
As a result of examining the NMR data, no broad singlet peak due to the proton of the amino group was observed, and it was confirmed that the starting material amino group was substituted with a chloropropenyl group. Additionally, shown below
From NMR data, 1,3-dichloropropene-1
It was confirmed that the chlorine at the 3-position had reacted with the amino group of the raw material. NMR chemical shift of chloropropenyl group NMR δ tms: 4.70 (2H, s) 6.20 (1H, s) 6.50 (1H, s) (Assuming that the chlorine at position 1 of 1,3-dichloropropene-1 has reacted, The chemical shift of the two protons of the methyl group to which chlorine is bonded shifts to the lower magnetic field side.) Compounds Nos. 6, 9, and 15 were identified in the same manner. In addition, in the production examples, formulation examples, and test examples, active ingredient compounds are indicated by compound numbers in Table 1.

【table】

[Table] For the compound of the present invention, the active ingredient compound represented by the above general formula () may be used as it is, but generally, depending on the purpose of use, it is mixed with a suitable liquid carrier (for example, an organic solvent). Dissolved or dispersed, or mixed or adsorbed onto a suitable solid carrier (eg diluent, filler). At that time, by adding various auxiliary agents (e.g. emulsifiers, stabilizers, dispersants, suspending agents, spreading agents, wetting agents, penetrating agents) as necessary, emulsions, wettable powders, granules, etc. It can be used in various dosage forms such as tablets and powders. The herbicide of the present invention can be used in combination with one or more other herbicides, pesticides such as insecticides, fungicides, plant growth regulators, soil conditioners, or fertilizing substances, as well as in combination with these. Mixed preparations are also possible. The content of the active ingredient in the herbicide of the present invention is 1 to 10% in granules, 20 to 80% in wettable powders, and 10 to 50% in emulsions.
% (all indicate weight %) is desirable. Next, examples of formulations of herbicides containing the compound of the present invention as an active ingredient will be shown, but the present invention is of course not limited to these. Formulation Example 1 Granules Compound (1) 5 parts, bentonite 72 parts, talc 20
1 part, 2 parts of sodium dodecylbenzenesulfonate, and 1 part of sodium ligninsulfonate, and after kneading with an appropriate amount of water, granulation was carried out in a conventional manner using an extrusion granulator to obtain 100 parts of granules. Ta. Formulation Example 2 Wettable powder 50 parts of compound (4), ±40 parts of diatomaceous powder and 10 parts of sodium dodecylbenzenesulfonate were mixed and ground to obtain 100 parts of a wettable powder. Effects The effects of the compounds of the present invention represented by the general formula () and herbicides containing them as active ingredients will be shown by test examples. Test Example 1 Paddy field weed control test R/5000 Wagner pots were filled with soil, and seeds of Japanese millet, firefly, and Cyper cyperus and tubers of Cyper spp. were sown and submerged in water. )
Two plants were used as one plant, and the two plants were transplanted and grown in a greenhouse. Three days after transplanting paddy rice, at the beginning of weed emergence, a predetermined amount of the test compound was submerged in water using a granule according to the method described in Formulation Example 1 above. One month after the treatment, weed growth and chemical damage to paddy rice were investigated, and the results shown in Table 2 were obtained. In this table, the degree of chemical damage to crops and the herbicidal effect on weeds are expressed by comparing the state of emergence or growth of crops or weeds with the air dry weight of untreated plots, according to the evaluation criteria below. Evaluation standard 0 vs. untreated area survival rate shown as air dry weight ratio 91-100% 1 61-90% 2 31-60% 3 11-30% 4 6-10% 5 0-5%

【table】

【table】

[Table] From the above results, the herbicide composition of the present invention has remarkable herbicidal activity against annual weeds and perennial weeds of the Cyperaceae family, and can be used at any time from before weed emergence to during the growing season. It is found to be effective and easy to use. As described above, the herbicidal composition of the present invention has a significantly wider range of usage periods and a herbicidal spectrum than conventional herbicides, and is therefore practically useful.

Claims (1)

[Claims] 1 General formula () (In the formula, R represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, or a phenoxy group, n represents an integer of 1 to 5, and R ¹ represents a lower haloalkenyl group or a lower haloalkynyl group. R ² represents a halogen atom). 2 In the general formula (), R is a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, an isopropoxy group, or a phenoxy group, and R ¹ is a 2-chloro-2-propenyl group, a 3-
Chloro-2-propenyl group, 2,3-dichloro-
2-propenyl group, 2-bromo-2-propenyl group or 3-iodo-2-propynyl group,
The compound according to claim 1, wherein R ² is a chlorine atom. 3 In the general formula (), R is a hydrogen atom, R ¹ is a 2-chloro-2-propenyl group, 3-
Chloro-2-propenyl group, 2,3-dichloro-
2-propenyl group, 2-bromo-2-propenyl group or 3-iodo-2-propynyl group,
The compound according to claim 1, wherein R ² is a chlorine atom. 4 In the general formula (), R is a fluorine atom, a chlorine atom, or a methyl group, and R ¹ is a 2-chloro-2-propenyl group, 3-chloro-2-propenyl group, 2,3-dichloro-2- propenyl group, 2
-bromo-2-propenyl group or 3-iodo-
The compound according to claim 1, which is a 2-propynyl group and R ² is a chlorine atom. 5 In the general formula (), R is a trifluoromethyl group, isopropoxy group or phenoxy group, R ¹ is a 2-chloro-2-propenyl group, 3
-Chloro-2-propenyl group, 2,3-dichloro-2-propenyl group, 2-bromo-2-propenyl group or 3-iodo-2-propynyl group, and R ² is a chlorine atom. A compound according to item 1. 6 General formula () (In the formula, R represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, or a phenoxy group, n represents an integer of 1 to 5, and R ¹ represents a lower haloalkenyl group or a lower haloalkynyl group. ^R2 represents a halogen atom) as an active ingredient.