JPS58192873A - 1,3,5-triazine derivative and herbicide containing the same - Google Patents

Abstract

NEW MATERIAL:The 2-alpha,alpha,beta,beta-tetrafluoroethyl-4,6-substituted-diamino-1,3,5 -triazine derivative of formula I [R1 is 1-4C alkyl; R2 is H or 1-4C alkyl; R3 and R4 are H, 1-4C alkyl or -C(O)R5 (R5 is 1-4C alkyl, monohaloalkyl, dimethylamino, etc.)]. USE:Herbicide exhibiting high activity either by soil treatment or by foliar treatment, and has selectivity to corn, soybean, etc. PROCESS:The compound of formula I can be prepared by reacting the compound of formula II with the compound of formula III in a solvent such as alcohol, DMF, etc. or in the absence of solvent, at 0-100 deg.C under atmospheric pressure- 10atm.

Description

DETAILED DESCRIPTION OF THE INVENTION Misfire 811 has the general formula:
, R4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -OR, and R is an alkyl group having 1 to 4 carbon atoms, a monohaloalkyl group, or a dimedelamino group,
2-α, which is a methoxymesolamino group),
The present invention relates to an α,β,β-tetrafluoroethyl-4,6-substituted diamino-1,3,5-)riazine derivative and a herbicide containing the same as an active ingredient.

The compound of the present invention is a novel 1.3.5-)IJ azine derivative, which is currently the most commonly used herbicide 2-chloro4.6-pisuethylamino 1,3.5
-triazine (simazine), 2-chloro-4-ethylamino-6-ipropylamino-1゜3.5-triazine (atrazine) and has the same basic structure.

The present inventors have recently demonstrated that 2-α,a,β,β-tetrafluoroethyl-4,6-substituted diamino-1,3,5-triazine derivatives can be used in corn, cereals, soybeans, and M.
It is safe for crops and selectively kills only weeds in areas where flowers and other crops are cultivated, as well as lawns, etc., and is particularly low in dosage, less than 11 times lower than the above-mentioned simazine, anthrazine, etc. It was discovered that the herbicidal activity was still as strong or stronger even when treated with the following methods, and this led to the completion of the present invention.

Recently developed herbicide 2-chloro-N-((4-methquin-6-methyl-1,3,5-)riazin-2-yl)
Aminocarbonyl]benzenesulfonamide, 5-[2
-Chloro-4-()Rifluoromethino・)Noenoki/]
-2-Nitrobenzoic acid sodium salt rc As shown in Figure 7', there is a strong desire to reduce the dosage of dangerous herbicides from the standpoint of protecting the environment.

The present inventors have focused on triazine thread compounds containing ummazine and atla// as substitute coating compounds, which have low toxicity to humans and livestock, 5 strong herbicidal action, and excellent selectivity. With the aim of expanding crop selectivity, we have investigated many compounds and compared the compound of the present invention represented by general formula [1] with atrazine in pre-germination, germination treatment salt/machine, and atrazine. It has been found that the herbicidal effect is more than twice as strong without compromising crop selectivity.

Generally speaking, most selective herbicides are soil-based herbicides, and there are very few foliage-based herbicides compared to kneads.

The compound of the present invention has a strong herbicidal effect against a wide range of weeds, without losing its efficacy even in small amounts, not only in soil treatment but also in foliage treatment, such as corn.

It is an extremely advantageous property to have selectivity for soybean clams.

The present invention has been completed based on these findings.

To describe the herbicidal action of the compound of the present invention in more detail, the compound of the present invention can be used for pre-emergence treatment of weeds, and for post-emergence treatment of weeds.
It also exhibits strong herbicidal activity against a wide range of upland weeds and paddy field weeds.For example, broad-leaved weeds such as plantain, Japanese knotweed, Japanese millet, pigweed, Japanese fir, morning glory, chickweed, yellowweed, waterweed, and azalea, as well as broad-leaved weeds such as seaweed and paddy grass. It has a strong herbicidal viscosity at low concentrations against various weeds such as Poaceae weeds such as , Japanese grasshopper, Foxtail grass, and Sparrow weed, and Cyperaceae miscellaneous species such as Cyperus japonica and Cyperus cyperus. As mentioned above, the main fl-! &niX'
It also boasts selectivity in soil treatment, stem and flower processing, and 8! Herbicides for deforestation, forests, and non-agricultural land (.

-But you can do something about it.

1k, the compound of the present invention has low toxicity to humans, animals, and fish.

In addition, it has a long 1JS efficacy and can maintain a longer period of time between 1 and 2 months compared to conventional triazine herbicides. [1]
Compound 11, which is also a compound 11, is also structurally similar and anti-compound, 2-) IJ Flu A lomethyl-4-ethylamino-6-inglobylamino 1.3.5-) Riazine [control compound (a) in the examples in his journal] is described in Japanese Patent Publication No. 36-19400@? According to
Although this compound has a higher herbicidal effect than commercially available triazine herbicides such as simazine and atrazine, it has a lower herbicidal effect than the compound of the present invention, and as shown in the examples, it is effective against most crops. Strongly indicates drug damage.

The compound of the present invention can be produced by the following method.

In addition, the alkyl group used in this specification shall include both a straight chain and a branched chain.

[In the formula, A represents a hydrogen atom or lower alkyl, R,
, R, , Tortoise, as defined in R4Vi age (however, -OR, excluded) The reaction raw material (1) is a compound known in the literature, and is a compound that adds an amine to dicyanamide sodium salt or dicyandiamide. Synthesized by the method (Ber, 62°1390 (1
929)).

This reaction is carried out in the presence or absence of a solvent at υ~10
It can be carried out at a temperature range of about 0° C., and it may also be carried out at a pressure of 1-1 normal pressure or up to about 10 atmospheres. Solvents used in this reaction include various I alcohols, N,
Examples include highly polar organic solvents such as 4-dimethylformamide and dimethyl sulfoxide, and aromatic solvents.

1 When R1 or ViR contains -OR, it can be synthesized by any of the following methods.

(Method A) [However, R1r R1r R3r R1 is as defined above. ] The reaction raw material [dish] is a triazine having 7 amide groups and an imino group made into a sodium salt using sodium hydride or the like.

This reaction is carried out at 0-100°C in the presence or absence of a solvent.
It can be carried out at a temperature of about Examples of the solvent used in the reaction include dichloromethane, chloroform, N-dimethylacetamide, and dimethylsulfoxide.

(Method B) H [However, R1, R2+ Rm * As defined before RI. ] This reaction is carried out in the presence or absence of a solvent in the range of 0 to 150
It can be carried out at a temperature of about °C. As the solvent used in the reaction, aromatic solvents such as benzene and toluene, tetrahydrofuran, dioxane, N,N-dimethylformamide, etc. can be used.

I will explain it in more detail by giving a specific example of a bad synthesis below,
It goes without saying that the scope of the present invention is not limited to these examples.

Synthesis Example 1 Inglobil biguanide 28v1 in 5Qiij flask
α,α,β,β-Tetrafluoropropionic acid lupropyl ester 3.8F, and ethanol 3'Qj+7
and stirred overnight at room temperature. Ethanol was distilled off under reduced pressure, and the resulting viscous liquid was washed with water to obtain the target product, 2-α.
, α, β, β-tetrafluoroethyl A-4-improvylamino-6-amino-1°3,5-1) White crystals 41 of amino were obtained.

Synthesis Example 2 2-a, α, β, β-tetrafluoroethyl-4-isopropylamino-6-amino-1,3
5-) After dissolving riazine 2 in total N,N-dimethylformamide, 0.42 f of sodium hydride (50%) was added and stirred overnight. After cooling, 1 vol of chloroacetyl chloride was added, and the mixture was stirred overnight at the same temperature, poured into ice water, and extracted with ether. The ether was distilled off under reduced pressure to obtain yellow crystals. Benzene: recrystallized from 1% hexane,
1.5 yt of pale yellow crystals of the target product, 2-α,α,β,β-detrafluoroethyl-4-inpropylamino-6-chlorothylamino-1,3,5-)riazine, were obtained.

Synthesis Example 3 2-α,α,β,β-tetrafluoroethyl-4-ingrobilaono-6amino-1, in 50jL/flask
3,5-) Two parts of IJ7 gin and one part of anhydrous vinegar were added, and the mixture was refluxed overnight. Carefully add water and add bicarbonate)
l) Acetic acid was made into a salt with an aqueous rum solution, extracted with ether, and the ether was distilled off under reduced pressure. The obtained white crystals were recrystallized from 2% benzene and hexane to obtain the target product, 2-α, α, β, β-tetrafluoroethyl-4-isopropylamino-6-acetylamino-1,3. ,5-
1.3 of the triazine was obtained.

Synthesis example 1 is shown below. 2. 3 and the structures and physical properties of the compounds of the present invention synthesized by methods similar to these and 1 instrumental analysis data.
It can be used for the purpose of selectively weeding corn, soybeans, cotton, rice, and other weeds such as barley, wheat, and barley, and it can be used to control the pre-emergence and post-emergence of these weeds. It can also be applied to the first one. The compounds of the invention can be used in a wide range of application rates, for example from 0.5 to 100 particles per are, preferably from Vi 1 to 509.

When actually using the compound of the present invention, the active substance itself can be dispersed, and any formulation form such as a wettable powder, emulsion, granule, or powder can be used.

In preparing these formulations, for example mineral powders (kaolin, bentonite, clay, montmorillonite, talc) are used as solid carriers.

Kuinou earth, back mother, vermicierite 1 gypsum.

Calcium carbonate, phosphorus, T:I ash, etc.), plant powders (soybean flour, Kotomo flour, Honsatsu, tobacco flour, starch, crystalline cellulose, etc.), polymer compounds (petroleum resin, polyvinyl chloride, (ketone resin, etc.) Furthermore, alumina, waxes, etc. Examples of liquid carriers include alcohols (methanol, ethanol, butanol, ethylene glycol, pendino alcohol, etc.), aromatic hydrocarbons (toluene, benzene, xylene, etc.), chlorinated hydrocarbons (chloroform, chloride vertical wood, monochlorobenzene, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ether ketone, / chlorhexanone, etc.), esters (ethyl acetate, butyl acetate, etc.), acid amides (N , N-dimethylacetamide, etc.), nitrites (acetonitrile, etc.), ether alcohols (ethylene glycol ethyl ether, etc.), and water.

Surfactants used for purposes such as emulsification, dispersion, and diffusion are:
Nonionic, strongly ionic, cationic and zwitterionic ones can be used.

Examples of surfactants used include polyoxy7 ethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxedele 7B'tdHl ester, vine and tan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, A-oxyethylene, oxybu-o-pyrene. Polymer, polyoxyethylene alkyl phosphate ester, fatty acid salt, alkyl sulfur ester salt, alkyl sulfo/#ni salt, alkylaryl sulfonate, alkyl phosphate ester salt, polyoxyethylene alkyl ester, quaternary ammonium These include salts, oxylalkyl amines, etc., but are of course not limited to these. Moreover, gelatin, casein, sodium alginate, starch, agar, polyvinyl alcohol, etc. can be used as adjuvants if necessary.

Hereinafter, a typical method of blending the compound of the present invention will be explained.

Blending method 1 (Preparation of irrigation agent) 25 parts of the compound of the present invention, 1 part of Tsurupol 5039 (manufactured by Toho Kaji Kogyo Co., Ltd., trade name) 5], and 70 parts by weight of Merck were thoroughly ground and mixed. Use as a hydrating powder.

Blending method 2 (Preparation of emulsion) 5 parts by weight of the compound of the present invention, 10 parts by weight of Tsurupol 3005X (manufactured by Toho Chemical Industry Co., Ltd.), 45 m of Atsushi-butanol
1 part by weight of xylene and 40 parts by weight of xylene were thoroughly mixed to form an emulsion.

Blending method 3 (granules!lil&) 1 part by weight of the compound of the present invention, 1 part of bentonite 451, clay 44] 1fiL&, 5 parts of sodium lignin sulfonate
1iIL and dodecylbenzenesulfonic acid) IJ
Thoroughly pulverize and mix 2 parts of Um 5-fold, add water and knead well, and then granulate and dry to form granules. ○ Compounding method 4 (Made by 1llll of powder) Compound of the present invention @ 1-fold its Fuyobi Clay 99 Thoroughly grind and mix the parts by weight to make a powder.

The usage of the herbicide of the present invention varies depending on the method of use, the place of use, and the target weed species, but it is usually sufficient to use 1 to 50 y (active ingredient) per 1 ar. Furthermore, the compound of the present invention can also be used in combination with other herbicides for the purpose of improving its efficacy as a herbicide, and a synergistic effect can be expected in some cases. For example, the following ingredients may be used.

Phenoxy herbicide 2. 4-Dichlorophenoquine acetic acid: 2-methyl-1-chlorophenoxe7acetic acid; Butyl-2-(4-(5-trifluoromethyl-2-pyridyloquine)phenoxy"propionate Zone ester (contains 5 itr of salt), etc.

(BJ phenyl ether-based removal agent 2.4-dichloride
Luphenyl-4'-nitrooxynyl ether; 2.4.
6-) Dichlorophenyl-41 nitrolophenyl ether; 2,4-dichlorophenyl-4'-nitro3'-
meth)xyphenyl ether; 2,4-dichlorophenyl-3'-methoxycarbonyl-4'-nitrophenyl ether; 2-chloro-4-trifluoromepurphenyl-3'-ethoxy-4'-nitrophenyl ether;
5-(2-chloro-4-() IJ fluoromethyl)
[phenoxy]-2-nitrobenzo-tIL tetrium salt, etc.

(0) Triazine herbicide 2-chloro-4,6-pisethylamino-1.3.5-
triazine, 2-chloro-4-ethylamino-6-ingrobylamino-1.3.5-) riazine: 2-methylthio-4,6-pisethylamino-1.3°5-triazine, etc.

(D) Urea herbicide 3-(3,4-dichlorophenyl)-1,1-dimethylurea; 3-(3,4-dichlorophenyl)-1-medoxyl-methylurea; 3-(a, α,α-trifluoro-tolyl)-1,1-dimethylurea; 3
-(4-(4-methylphenethyloxy)phenyl)-
1-Methoxy-1-methylurea; 3-(5-t-
butyl-3,4-thiadiazol-2-yl)-4-hydroxy-1-methyl-2-imidazolitone and the like.

(→Carbamate yarn herbicide inpropyl-N-(3-chlorophenyl) carbamate, methyl-N-(3,4-dichlorophenyl) carbamate: 4-chloro-2-butynyl-N-(3-chlorophenyl) Carbamate, etc. 0 (F) Thiol carbamate type removal agent I-ethyl-N,N-hexamethylenethiol carbamate; y-(4-chlorobenzyl)-N,N-7 ethyl tesul carbamate; I-ethyldiglobil thiolcarpamate etc.

(()) Anilide thread herbicide 3.4-dichloroglobionoanilide; N-methquinmethyl-2,'6'-dimethyl-2-chloroacetanilide, 2-chloro-2,'6'-diethyl-N- )-acetanilide, 2-chloro-2',6
'-Diethyl-N-(broboxy/ethyl)-acetanilide; α-(2-naphthoxy7)gropionoanilide, and the like.

04J Uracil herbicide 5-bromo-3-see-butyl-6-methyluranyl: 3-brohekiflu-5,6-toIJ methyleneuracil.

(I+Lepyridinium salt herbicide 1.1'-dimethyl-4,4'-dipyridinium dichloride; 1,1'-ethylene-2,2'-dipyridinium dibromide, etc.

(J) Phosphorus-based removal agent N-(phosphonomethyl)gly7rin: --ether-0-(
2-Nitro-5-methylphenyl)-N-11-butylphosphoramidothioate; O-methyl-〇-(2-
7-(2-Methyl-1,1-piperidylcarbonylmethyl)-0,0-di-globildithiophosphate: (2-amino- 4-methylphosphino-butyryl)-alanylalanine monosodium salt, etc.

(Phantom toluidine unveiling agent α,α,α-trifluoro2,6-sinitro N,N
-dipropyl-P-toluidine; N-(cyclopropylmethyl)-α,α,α-trifluoro2,6-dinitro N-propyl-P-toluidine.

(L) Other herbicides 5-t-butyl-3-(2,4-dichloro-5-improboquinophenyl)-1,3,4-oxadiazoline-
2-off. 3-isopropyl-2,1,3-benzothiadiazinone-4,2,2-dioxide: 2-(a-
(butoxy)-N,N-jethylglobionamide:
3-Amino-2,5-dichlorobenzoic acid: 4-(2,4
-dichlorobenzoyl) -1,3-dimethinohylazol-5-yl-P-toluenesulfonate: 2-chloro-N-((4-methoxy/-6-methyl-1,3,5
-) riazin-2-yl)aminocarbonyl]benzenesulfonamide, etc.

The above is merely an illustration, and it goes without saying that other herbicides that can be used in combination with the compound of the present invention are not limited to these. The herbicide of the present invention may also include pyrethroid insecticides, sono and other insecticides,
It is also possible to use it in combination with plant #7 JII4 nodules, microbial pesticides, and fertilizers.

Next, an example of compound #A of the present invention will be presented to further clarify the present invention, but it goes without saying that the scope of the present invention is not limited to this example.

Wiping Experiment Example 1 In a greenhouse, a 1/2500 are volume of field soil was prepared, and the following plants were grown there. As weeds, weed grass and foxtail grass.

Pigweed, dogbini. Japanese knotweed, plantain, and blue knotweed, as well as sweet corn, soybeans, and cotton.

The various pre-germination treatments mentioned above are carried out 24 hours after planting the plant seeds.
2 to 109 doses per are were applied at time i.

The post-germination treatment was carried out 10 to 14 days after sowing the plant seeds and before germination at the 2- to 3-leaf stage of the crabgrass. The condition of the plants was observed 20 days after the treatment, and the results are shown in the table below.

The values in the table are based on the following criteria.

5: Complete suppression 4: 80% suppression 3: 60% suppression 2: 40% suppression: 20qb suppression
O: No effect The spraying method was to dilute 25% hydrating powder with 15 tons of water per area and spray it with a glass sprayer.

Margin below

Claims (1)

[Scope of Claims] 1 General formula: (However, in the formula, R is a lower alkyl group having 1 to 4 carbon atoms, R
8 is a water "JA atom or a lower alkyl group having 1 to 4 carbon atoms, R,, R, is a hydrogen atom, and the cumulative number is 1 to 4σ) 1 lower alkyl group -OR, and R is a lower alkyl group having 1 to 4 carbon atoms. 4 alkyl, mono-roalkyl group, dimethylamino group, methoxymethylamine group)
-α,α,β,β-tetrafluoroether-4,6-f
ill-converted diamino-1,3,5-) riazine derivative. 2 general formula: (However, in the formula, R1 is a lower alkyl group having 1 to 4 carbon atoms, R
1 is a hydrogen atom or a lower -/alkyl group having carbons X01 to 4, R,,R,i hydrogen atom, a lower alkyl group having 1 to 41 carbon atoms, or -0R- and R1 is a vertical prime number of 1 to
2-a, α, β, β-tetrafluoroether-4,6 represented by 4 alkyl, 10 alkyl group, dimethylamino group, methoxymethylamine group)
-rIt-substituted diadiamino, 3.5-) riazine I4
A herbicide that is contained as an active ingredient.