JPS58144389A - 1h,5h-(1,2,4)triazolo(1,2a)(1,2)-diazepine derivative, its preparation and herbicide containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formulaI(X is Cl or Br; R is 1-3C alkyl; Y is O or S). EXAMPLE:2-(4-Chloro-2-fluoro-5-methoxyphenyl)-1H,5H-(1,2,4)-triazolo-[ 1,2a][1, 2]-diazepine-1,3(2H)-dione. USE:Herbicide having excellent selectivity to protect the crops such as soybean, cotton, wheat, corn, rice plant, etc. from the harm of weeds, and to keep good harvest. It exhibits excellent activity at low rate of application. PROCESS:The compound of formulaI(wherein Y is O) is prepared by reacting the urazole derivative of formula II (M is alkali metal) with 1,5-dihalopentane.

Description

Detailed Description of the Invention The present invention is based on the general formula TI) (wherein, X represents a chlorine atom or a bromine atom, Y represents an oxygen atom or a sulfur atom, and K represents a lower alkyl group having 1 to 3 carbon atoms. .) IH,5H-(1,2,4))ria1zolo[1,2 turtle)(1,2)-diazepine derivative (hereinafter referred to as the compound of the present invention), its production method, and its production method It relates to a herbicide contained as an active ingredient.

The present inventors have studied soybean, cotton, wheat, corn,
As we continued our research with the aim of developing a highly active herbicide with excellent selectivity that would protect important crops such as rice from weed damage and maintain high yields, we discovered that the herbicide represented by general formula (I) The present invention was completed after discovering the excellent properties of the invented compound, which has an excellent weight removing effect and hardly harms important crops such as soybeans and cotton.

Certain 2-phenyl-(1,2,4))riazolo(1
, 21(1,2) diazepine derivatives have herbicidal activity as shown in JP-A-50-160429. However, compared to the similar compounds described in the publication, the compound of the present invention has a much superior herbicidal effect, as is clear from the examples below, and has a significantly superior herbicidal effect on annual and perennial weeds in fields and paddy fields. Alternatively, post-emergence treatment can show extremely high herbicidal effects with just a paper dose.

Next, the method for synthesizing the compound of the present invention will be described.

1.2. Regarding the synthesis method of 4-triazole derivatives,
Heterocyclic compound vol 37 ('
) detailed in W.W.W. and Son). The compound of the present invention can be synthesized according to the following formula I.

(Capital) (V) ([vl @) (III (In the formula, X and k are the same as above.) General formula (
The dithiourazole derivative of Ill is prepared by mixing the urazole derivative of general formula
Obtained by processing for 10 hours.

The urazole derivative of the general formula (i[) is produced by alkali metallizing the urazole derivative of the general formula with a metalizing agent such as sodium methoxide, sodium hydride, butyl lithium, etc., and then converting it to a dihalopentane such as 1,5-dibromopentane. It is synthesized by heating in the presence of a polar aprotic solvent such as dimethylformamide or dimethylsulfoxide, if necessary.

Urazol derivative meter) is Organifuku Synthesis 5
1 121 (1971) from 7-enyl isocyanate (b).

This incyanate (funded) is published in the Journal of the American Chemical Society (J, Am.

□ 2-chloro-4-fluorophenol or 2-chlorophenol described in Chem, Soc, ) 81 94 (1959)
It can be obtained by alkyl etherifying -bromo-4-fluorophenol, nitration with nitric acid-sulfuric acid, and reduction with hydrogen, and reacting the obtained aniline with phosgene. Alternatively, it can also be obtained by converting phenol into a carbonate ester, nitrating it, hydrolyzing the carbonate ester, etherifying it, and then reacting the resulting aniline with phosgene.

Next, examples will be shown to explain the compounds of the present invention in more detail.

Example 1 2-(4-chloro-2-fluoro-5-methoxyphenyl)-1H,58-(1,2,4)-triazolo(1
t21) (1,2)-Diazepine-1,3(2H)-dione (compound number (1)) Dissolve 0.46 F of metallic sodium in 20-methanol and heat it to 4-(4-chloro-2 -71 Luoro-5-methoxyphenyl)-urazole 2.6F
was dissolved, and methanol was concentrated under reduced pressure. The residue was dissolved in dimethylformamide 20-1, 2.3 P of 1,5-dibromopentane was added, and the mixture was stirred at 110 to 120°C for 4 hours. After cooling, water was added and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography and further recrystallized from methanol to give a 0.
Colorless crystals of 42 F were obtained. mP 121.5
~123°C IR sea, 1750, 1680 C-sheet Example 2 2-(4-bromo-5-ethoxy-2-fluorophenyl)-1H,5H-(1,2,4) triazolo(1,2
1&](1,2)-diazepine-1,3(2H)-dithione (compound number (5)) 2-(4-bromo-5-ethoxy-2-fluorophenyl) -18,5H-(1,2 ,4) Triazolo (1,
21) Dissolve 0.63 F of (1,2)-diazepine-1,3(2H)-dione in xylene 10-
Phosphorus trisulfide (F) was added and the mixture was refluxed for 8 hours. Insoluble matter was separated by furnace, and xylene was distilled off under reduced pressure. The residue was crystallized and washed with methanol to obtain colorless crystals of 0.65 f.
P 173-5~174-5℃IRν -i 12
90 C theory According to Example 1, compounds (1), (2), and (3) in Table 1 were added to +41, +51, and +41 in Table 1 according to Example 2.
Compound (6) was synthesized.

Table-1 The spectral data of the compounds in Table-1 are shown in Table-2. The compound numbers are the same as those listed in Table-1.

Table-2 Compound number ill IRvan 1750, 16
8ONMRδPPm 1.8 (6H, m), 3
．． 9(3H,5)f2+ 1Rνα 1750
, 1680(3) IRvcs 17
50, 168ONMRδPPm 1.0(3
H, t), 1.75 (6H.

”) e 3-9 (2H, t) 141 1Rycn 11290' NMRδPPm 3.85 (3H, 1) (511Rν
cm' 1290 When the compound of the present invention is actually used, it is formulated into easy-to-use forms such as emulsions, wettable powders, suspensions, granules, and powders in accordance with the usual methods in the agricultural chemical formulation field. is common.

In this case, the content of the compound of the present invention in each formulation is 0.1 to 90 degrees, preferably 1 to 8 degrees.

Examples of solid carriers for preparing these pharmaceutical products include kaolin, bentonite, talc, diatomaceous earth, gicrite, and synthetic hydrous silicon oxide. Examples of liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, ketones such as cyclohexanone and inholone, chlorobenzene, dimethylformamide, cellosolve, ethylene glycol, and water. Examples of surfactants used for purposes such as emulsification, dispersion, and spreading include polyoxyethylene alkyl ethyl, polyoxyethylene alkylaryl ether, polyoxyethylene styryl aryl ether, polyoxyethylene fatty acid ester, and polyoxyethylene alkylaryl ether. Examples include nonionic surfactants such as oxyethylene sorbitan fatty acid esters and oxyethylene oxypropylene polymers, and anionic surfactants such as alkyl sulfate salts, alkyl sulfonates, dialkyl sulfosuccinates, and alkylaryl sulfonates. These may be used alone or in combination.

Furthermore, if necessary, a lignin sulfonate, polyvinyl alcohol, or a cellulose derivative such as methyl cellulose can be used as an adjuvant. Of course, the carriers, surfactants, etc. that can be used are not limited to those shown here.

Next, a detailed explanation will be given by giving a formulation example, but it goes without saying that the formulation ratio and carrier can be changed. Note that parts in each example indicate parts by weight.

Formulation Example 1 Compound (1180 parts, 7 parts of polyoxyethylene alkylaryl ether and 1 part of synthetic hydrated silicon oxide)
5 parts were thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 2 2110 parts of compound +7 parts of polyoxyethylene alkylaryl ether, 3 parts of alkylaryl sulfonate and 80 parts of cyclohexanone are thoroughly mixed to obtain an emulsion.

Formulation Example 3 1 part of compound (5), 1 part of synthetic hydrous silicon oxide, 5 parts of lignin sulfonate and 93 parts of clay are thoroughly ground and mixed, water is added and the mixture is thoroughly kneaded and then granulated and dried to obtain granules. .

Formulation Example 4 3 parts of compound (1), 0.5 parts of isopropyl phosphate, 66.5 parts of clay and 30 parts of talc are thoroughly ground and mixed to obtain a powder.

Formulation Example 5 15,320 parts of the compound was mixed with 60 parts of an aqueous solution containing 3% by weight of polyoxyethylene sorbitan monooleate,
A suspension preparation is obtained by mixing 20 parts of an aqueous solution containing 3 parts by weight of sodium alginate as a dispersion stabilizer with the active ingredient wet-pulverized until the particle size becomes 3 μm or less.

When the compounds of the present invention are used either pre- or post-emergence, the application rate can vary over a fairly wide range, but is usually between 0.1 and 50 F per are, preferably 0 J-
It is 30F.

Furthermore, the compound of the present invention can be used in combination with other herbicides in order to improve its effectiveness as a herbicide, and a synergistic effect can be expected in some cases. Examples of this include, for example, 2,4°-dichlorophenoxyacetic acid (2,4-D) i
(2,4-DB); 2-(2-methyl-4-chlorophenoxy)propionic acid (mecoprop); Methyl 2-
(4-(2,4-dichlorophenoxy)phenoxy]propionate (diclofopmethyl); butyl-2-[
4-(5-trifluoromethyl-2-pyridyloxy)
Phenoxy] propionate (fluazifop butyl)
i2-(4-(3,5-dichloro-2-pyridyloxy)phenoxy) phenoxy series (including esters and salts) such as propionic acid, 2,4-dichlorophenyl-4'
- trophenyl ether); 2,4.6
-) dichlorophenyl-4'nitrolophenyl ether (chlornitrophen); 2-chloro-4-trifluoromethylphenyl-3'-ethoxy-4'-nitrophenyl ether (oxyfluorophen); Chlorphenyl-4'-2) O-3'-methoxyphenyl ether (chloromethoxynyl); 2,4-dichlorophenyl-3'-methoxycarbonyl-4'-2) lophenyl ether (bifenox); Diphenyl ethers such as 5-[2-chloro-4-(trifluoromethyl)phenoxyph-2-nitrobenzoic acid (acifluorophen), 2-ri0k-4,5-bisethylamine y = 1° 3.5-1 riazine (simazine); 2-
Chlor-4-ethylamino-6-isopropylamide/-
1,3,5-)Ryazine (Atrazine); 2-Methylthio-4,6-pisethylamino-1,3.5-)Ryazine (Simetrine); 2-Methylthio-4,6-pisisopropylamino-1.3 , 5-) riazine (promethrin); 2-chloro-4,6-pis-imbrobylamino-1,3.5-) riazine (propazine); 2-(2-chloro-4-ethylamino-5-) riazin-6-ylamino)2-methylpropionitrile (cyanazine); 4
-amino-6-tert-butyl-3-methylthio-
1,2,4-) riazin-5(4H)-one (metrypsin); 3-cyclohexyl-6-dimethylamino-1-methyl-8-) riazin-2,4-dione (hexazinone); 2- Methylthio-4-ethylamino-6-isopropylamino-1,3,5-triazine (amethrine); 2-methylthio-4-(1,2-dimethylpropylamino)-〇-ethylamino-1,3,5-triazine (dimetamethrine); 4-amino-3-methyl-6-
7-enyl-1,2.4-triazin-5(4H)-one (methamidron), 3-(3,4-
dichlorophenyl)-1,1-dimethylurea (diuron); 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (linuron); 1-(2,2-
Dimethylbenzyl)=3-P-)lylurea (Daimeron); 1゜1-dimethyl-3-(3-)lifluoromethylphenyl)urea (fluoromechelone); 3-(4=
Bromo-3-chlorophenyl)-1-methoxy-1-methylurea (chlorobromulon); 3-(4-(4-
chlorophenoxy)phenyl)-1,1-dimethylurea (chloroxuron); 3-(4-isopropylphenyl)-1,1-dimethylurea (improturon);
3-(2-Benzothiazolyl)-1,3-dimethylurea (methbenzthiazuron); 3-(5-tertiary-
Butyl-3,4-thiadiazol-2-yl)-4-hydroxy-1-methyl-2-imidazolitone (putidazole); 3-(3-chloro-4-methoxyphenyl)-1
, urea-based products such as 1-dimethylurea (methoxuron),
Isopropyl-N-(3-chlorophenyl)carbamate (chloropropham); Methyl-N(a p 4-dichlorophenyl)carbamate (Swef 7”) 94-
Methyl-N-(4-
Aminobenzenesulfonyl) carbamate (Ashram); 3-isopropoxycarbonyl-aminophenyl-
Carnolyte series such as N-ethyl carbanilate (FAM'/77A), 5-(4-chlorobenzyl)-N,N
9 Ethylthiol carbamate (penthiocab); s-
Ethyl-NN-hexamethylenethiol carnolyte (
molinate); S-ethyl-N, N-gen-furovirthiolcarbamay) (EPTC); S-ethyl-
N,N-diisobutylthiol carbamate (Buticy); 5-n-propyl-N,N 9 n 7-
Lopylthiol carbamate (Barnathy);
S-2,3゜3-Trichloroallyl-N,N-diisopropylthiolcarbamate (trialate); S-ethyl-N-ethyl-N-cyclohexylthiolcarbaite (cycloate);
N,N-di-secondary butylthiol carbamate (
thiol carbamate series such as thiocarbasil), 3,
4-Dichloropropionanilide (Furohanil); N-
Methoxymethyl-2,6-dinithyl-chloroacetanilide (alachlor); 2-chloro-2',6'-
Diethyl-N(butoxymethyl)-acetanilide (phthaclor); 2-chloro-N-(2-ethyl-6-methyl-phenyl)N-(2-methoxy-1-methylethyl)acetamide (metolachlor); N -Chloroacetyl-N-(2,6-')ethylphenyl)-chrysin ethyl ester (diethyl); 2-chloro-N-isopropylacetanilide (frovacrol) iN,N-
Dimethyl-2,2-diphenylacetamide (sifuenamide); N-naphthylphthalamic acid (naptalam); N-(lsl-dimethylpropynyl)-3,s
-dichlorobenzamide (furonamide); ethyl-N-
Benzoyl-N-(3,4-dichlorophenyl)-2-
Aminopropionate (benzoylprop); Methyl-N-benzoyl-N-(3-chloro-4-fluorophenyl)-2-aminopropionate (plumprop); 5'-()lifluoromethanesulfonamide)
Aceto 2#, 4f-xylidide (mefluidide)
Amides such as 5-bromo-3-secondary-phthyl f! -Methyluracil (bromacil) 5-chloro-6
- Uracil series such as methyluracil (Turbacil), 2
,5-dichloro-3-aminobenzoic acid (chloramben)
;3゜6-dichloro-2-methoxybenzoic acid (Dicamba); Dimethyltetrachlorothyrephthalate) (DCP
Benzoic acid series such as A), N,N-bis(phosphonomethyl)glycine (glyphosate)); 0-ethyl-〇-(2
-Nitro-5-methylphenyl)-N-Secondary Butyl Phosphoronamidothioate (Butamiphos) 95-
(2-methyl-1-piperidylcarbonylmethyl) 0
, O-C n-propyldithiophosphate (Biperophos); phosphorus-based, α, such as 0,0-diisopropyl-5-(2-benzene-sulfonylaminoethyl)phosphorodithioate (Penzlide);

α,σ-trifluoro-2,6-sinitro-N,N-dipropyl-p-toluidine (trifluralin) i3,4
-dimethyl-2,6-sinitro-N-1-ethylpropylanilide (bendimethalin); α,α,α-trifluoro-2,6-dinitro-N-propyl-N-cyclopropyl-P-)cyidine (profluralin) Toluidine series such as i4-(methylsulfonyl)-2,6-sinitro N, N-dipropylaniline and traline), arsenic such as monosodium methane arsonate (DSMA); system,
Maleic hydrazide (MH); 3-(2,4-dichloro-5-isopropoxyphenyl)-5-tert-
Butyl-3,4-oxadiazol-2(3H)-one (oxacyacin); 2-(3,4-dichlorophenyl)-4-methyltetrahydro-1,2°4-oxadiazole-3,5-dione (Methazole); 3-isopropyl-IH-2゜1.3-benzothiadiazine-+41
-38-one-2,2-dioxide (pentacine); 4
-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol-5-yl-P-) diazine series such as luene-sulfonate (pyrazolium), 4-amino-3
, 5,6-dolichloropicolinic acid (picloram); pyridine-based compounds such as 1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-pyridin-4(IH)-one (fluridone) , 2,6-dichlorobenzonitrile (dichlobenyl), 3,5-thiodo-4
-Hydroxybenzonitrile (aioxynil); 3,
Nitriles such as 5-dibromo-4-hydroxybendonitrile (bromoxynil), 2,2-dichloropropionic acid (Daravon); fatty acids (salts) such as 2,2,3,3-tetrafluoropropionic acid (Tetrapion); ), α-(β-naphthoxy)propionanilide (naproanilide); 1゜2-dimethyl-3,5-diphenyl-IH-pyrazolium methyl sulfate (diphensoquat); 2-methyl-4-phenyl Sulfonyltrifluoromethyl-sulfoanilide (perfluidone); 3-amino-1°2.4-) lyazole (amitrol); 4-chloro-5-methylamino-2-(3-
trifluoromethylphenyl)pyridazine-3(2H)
-one (norflurazone); 2-secondary-butyl-
4,6-cinitrophenol (dinoseb); 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl methanesulfonate (ethofumesate); 5
-amino-4-chloro-2-phenyl-pyridazine-3
(2H)-one (pyrazone); 1,1'-dimethyl-4,4'-bipyridylium dichloride (paraquat); 1,1"-ethylene-2,2'-bipyridylium dibromide (Daiko) ); 2(1-(N-allyloxyamino)-butylidene)-5,5-dimethyl-4-methoxy-carbonyl-cyclohexane-1,3-dione Nλ salt (aloxydimusodium); 2-(N -ethoxybutyridyl)-5-(2-ethylpropyl)-3-
Hydroxy-2-cyclohexen-1-one; 2-chloro-N [(4-methoxy-6-methyl-1,3,5-)
Examples include riazin-2-yl)aminocarbonyl]benzenesulfonamide (chlorosulfuron),
It is not limited to these.

The compound of the present invention can be used in combination with insecticides, nematicides, fungicides, plant growth regulators, fertilizers, etc., if necessary.

Furthermore, the compound of the present invention may be used as an insecticide, nematocide, or
Mixtures with fungicides, plant growth regulators and fertilizers are also possible.

The compounds of the present invention will be explained in more detail by giving examples related to suboptimal ζ herbicidal efficacy.

Note that the control compounds in the examples are shown in Table 3.

Table 3 All evaluations of chemical damage to crops and efficacy against weeds in each of the following Examples were expressed as evaluation values using integers from 0 to 5 in accordance with the criteria described below.

The fresh weight of the above-ground parts of the plants that remained withered at the time of the survey was measured, and the ratio (%) compared to the untreated area was calculated.
Regarding crops and weeds, the chemical damage and herbicidal efficacy were evaluated using numbers from 0 to 5 based on the criteria shown in the table below.

Example 3 Field field pre-germination soil treatment efficacy comparison test Diameter 10
α, A cylindrical plastic beaker with a height of 10 m was filled with field soil, and weed seeds of millet, oat, marpa morning glory, and Japanese yam, and crop seeds of soybean and cotton were sown. After covering with soil, a predetermined amount of the raw material was made into an emulsion, diluted with water, and the soil was treated with a hand sprayer. After that, they were grown in a greenhouse, and the herbicidal efficacy was observed on the 20th day after treatment, and the results are shown in the table below.
4.

Table 4 Harmful water: Example 4 Post-emergence treatment test Tubers of Japanese sedge were planted in plastic pots with an inner diameter of 10 as and a height of lOc and grown for 4 weeks in a greenhouse. Seeds of barnyard grass, oat, wild mustard, and Japanese crocodile were sown in separate pots of the same type and grown in a greenhouse for two weeks. The treatment agent is formulated into an emulsion, dispersed in a predetermined amount in water (including a spreading agent), and applied to the foliage with a hand sprayer over the above two types of pots at a rate of 5 liters per area and 1 cloth. did. After being grown in a greenhouse for 3 weeks after the chemical treatment, each plant was examined for herbicidal efficacy. The Japanese perilla was kept in the greenhouse for an additional two weeks, and the number of regenerated shoots was measured and compared with the untreated plot. Efficacy evaluation was carried out using A for no regeneration at all, B for regeneration of 1-10% of the untreated plot, B for regeneration of 11-50 cm, and D for 151 cm or more.

These results are shown in Table-5.

Table 5 Example 5 Pre-germination treatment test A plastic tray with a length of 35 cm, a width of 25 cm, and a height of 15 cm was filled with upland soil, and the following were used to prepare a plastic tray containing field soil.
Weeds of brilliance, blueberry, Seiban sorghum and hackberry and soybean were sown. A predetermined amount of the hydrating agent was actually dispersed and sprayed over the entire surface of the soil using a small sprayer from above the tray at a rate of 5 liters per area. After the treatment, the plants were placed in a greenhouse for 20 hours and their chemical damage and leather removal efficacy were investigated. The results are shown in Table-6.

Claims (3)

[Claims] (1) General formula (wherein, X is a chlorine atom or a bromine atom, or has a carbon number of 1
~3 alkyl group, Y represents an oxygen atom or a sulfur atom. ) IH,5H-(1,2,4))riazolo[1
, 2-rich) (1,2)-diazepine derivatives. (2) A urazole derivative represented by the general formula (wherein, X represents a chlorine atom or a bromine atom, M represents an alkali metal atom, and H represents a lower alkyl group having 1 to 3 carbon atoms) and 1.5- A general formula characterized by reacting with dihalopentane (wherein, X is a chlorine atom or a bromine atom, and the trap has 1 carbon
-3 represents a lower alkyl group. ) IH,5R-(1,2,4))riazolo(t
, 2m1(1,2)-diazepine derivative manufacturing method. (3) General formula (wherein, X is a chlorine atom or a bromine atom, and the trap has 1 carbon atom)
-3 represents a lower alkyl group. ) IH,5H-(1,2 ,4)) Riazoro (1,2m)
[1,2)-Production method of diazepine derivative. +41-GE・. IH,5H-(1,2,4 ))
A herbicide characterized by containing a riazolo(1,21)(1,2]-diazepine derivative as an active ingredient.