JPS6011466A - Novel heterocyclic compound and herbicide - Google Patents

Abstract

NEW MATERIAL:A heterocyclic compound shown by the formula I (X is O, S, S, or NH; Y is halogen, n is 0-2; R is acryl, carbamoyl, sulfonyl, alkoxycarbonyl, or alkali metal). EXAMPLE:2-Cyano-3-methoxycarbonyl-benzothiophene. USE:A herbicide. Showing high herbicidal activity against a wide range of weeds such as large crab-grass, Echinochloa crus-galli Beauv., etc., effective against weeds immediately before germination or in an early stage of their growth. 2-20kg/ha application amount calculated as an active ingredient can wilt weeds 1-2 weeks after application, or limitation of an application amount or use of a proper method can use the herbicide as a selective herbicide for cultivating a specific crop such as maize, etc. PREPARATION:For example, a compound shown by the formula II is heated under reflux in an alcoholic solvent in the presence of an alkali to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel heterocyclic compound represented by the following general formula and a herbicide containing the compound as an active ingredient.

General formula (LX is 0, S, NH; Y is halo; B is an integer of O to 2; R represents alkyl, acyl, carbamoyl, sulfonyl, alkoxycarbonyl, or an alkali metal.) The heterocyclic compound represented by the general formula is a new compound that has not been published in literature, patents, etc., and as a result of its synthesis and various studies, it was found to have excellent effects as a herbicide.

That is, the compound of the present invention exhibits strong herbicidal activity against a wide range of weeds, and the active ingredient is applied at a dosage of 2 to 2 kg per hectare immediately before the weeds germinate or at an early stage of their growth.
When applied 0 to 9 times, it is possible to kill a wide range of weeds as described below in about 1 to 2 weeks.

In addition, by limiting the amount of this compound applied or applying an appropriate application method, specific crops such as corn, potatoes, sugarcane, peanuts, soybeans, sunflowers, barley, wheat, fulgum, paddy rice, cotton, and fruit trees can be controlled. Weeds can be selectively controlled in cultivated fields.

Typical examples of the compounds of the present invention include those shown in Table 1.

In addition, the compound is indicated by the symbol d in the above general formula, and in the physical properties column, the dark side is the nuclear magnetic resonance spectrum, the parentheses are the solvent, mp is the melting point, and η. indicates the refractive index, and the display method followed the conventional method.

The compound of the present invention can be synthesized, for example, according to the following formula.

Usually heated to reflux using an alcohol solvent or sodium alcoholade as a catalyst. toluene, benzene.

00-150' in strong bases such as sodium alcoholade, sodium hydride, potassium tash butoxide, in THF, dioxane, ether.

Preferably, the reaction is carried out at a temperature of 0° to 100°C.

Synthesis example (anhydrous ethanol solution containing sodium methylate of methylthiosalicylic acid ester soga271)
It was added dropwise into 0 ml. After that, while cooling with water, 36.5
Chloracetonitrile (F) was added dropwise, and the mixture was then refluxed for 1.5 hours. The salt generated during heating was removed using a p-filter, and when the solution F was cooled on ice, crystals were crystallized. If we take this t-F, then 8
3II, methyl 2-(cyanomethylthio)-benzoate was obtained. Add 20g of this to anhydrous eta/-/I/80
The mixture was placed in a solution containing 2.919 C+ sodium per milliliter and refluxed for 2 hours.

The solvent was distilled off, methylene chloride was added, and the resulting crystals were separated and diluted with water. When the aqueous layer was made acidic, yellow crystals were precipitated. The number of households is 14. Obtained r target objects. When recrystallized from a benzene-ethanol mixed solvent, it was found to be pale yellow needle crystals with a melting point of 176.5°C and sublimable. (Compound Flat 1) (2) A mixture of 183 g of methyl 5-chlorosalicylate and 350 ml of methyl ethyl ketone and 166 g of potassium carbonate was stirred well and cooled with water.
200 ml of a solution of methyl ethyl ketone containing 2.5.9 g of chloroacetonitrile and 2.5.9 g of potassium iodide was added dropwise.

The mixture was stirred at room temperature for 2 hours, and refluxed for an additional 2 hours to remove the generated common salt. The solvent was evaporated, ether was added, washed with caustic soda water and then water, and the solvent was evaporated to give the product 132I. Distilling this gives 135'/2
．． A fraction 106.9 of 5 trs Hg was obtained.

This was methyl 5-chloro-2-7 anomethoxybenzoate. This 50F was added to 300 mA' of absolute ethanol containing 6.6 I of sodium, refluxed for 2 hours, the solvent was distilled off, water was added, the aqueous layer was washed with methylene chloride, and the aqueous layer was acidified with hydrochloric acid. White crystal 44
I got a 9. When recrystallized from a water-methanol mixed solvent, it showed a melting point of 211°C.

(Compound A, 9) (3) 6 g of N-cyanomethylanthranilic acid methyl ester was added to 1.9 ml of absolute ethanol with 4
01 and refluxed for 2 hours. The solvent was distilled off, water was added, the aqueous layer was washed with methylene chloride, the aqueous layer was neutralized with hydrochloric acid, acidified with acetic acid, extracted with methylene chloride, and the solvent was distilled off to obtain a dark brown product 3.9. Ta. When this material is chromatographed using Florisil (hexane-benzene solvent),
Yellow crystals with a melting point of 147-149°C (Compound 11)
Add 1.5 g of bivaric anhydride to 10 benzofuran 2I, add 1 drop of pyridine, and mix in a water bath for 2 hours.
heated for an hour. Methylene chloride was added, the mixture was washed with aqueous caustic soda, water, and aqueous hydrochloric acid, and the solvent was distilled off to obtain 1.9I of the target compound (compound A23).

When recrystallized from a hexane-benzene mixed solvent, the melting point is 12.
9. ．． It showed 5°C.

The compound of general formula (■) exhibits strong herbicidal activity against a wide range of weeds, and the active ingredient is applied at a rate of 1 to 20% per hectare immediately before the weeds germinate or at the early stage of their growth.
When applied for 9 days, it is possible to kill a wide range of weeds as described below in about 2 to 3 weeks.

In addition, by limiting the amount of this compound applied or by applying an appropriate application method, it is possible to target specific crops such as corn, potatoes, sugarcane, peanuts, soybeans, sunflowers, barley, wheat, vines, cotton, and fruit trees. Weeds can be selectively controlled in fields where crops are cultivated.

Typical examples of the compounds of the present invention include those shown in Table 1.

The active compounds according to the invention can be formulated into dosage forms such as emulsions, wettable powders, pastes, and powders, by applying conventional formulation methods.

Furthermore, the compounds of the present invention can be mixed with other herbicides. Furthermore, in order to expand the range of action, it can be used in combination with agricultural chemicals other than herbicides, such as insecticides and fungicides.

Next, examples of typical dosage forms will be given. "Department" in the description
indicates parts by weight.

Example 1. As active ingredients for a wettable powder, 50 parts of the compounds shown in Table 1, 10 parts of diatomaceous earth, 35 parts of clay, 3 parts of sodium polyoxyethylene alkyl allyl ether sulfonate, and 2 parts of sodium alkylnaphthalene sulfonate were mixed and ground. A hydrating powder containing 50 parts of the active ingredient compound is obtained.

Example 2: When used, the solution is diluted with water to a predetermined concentration and sprayed. 15 parts of the compounds shown in Table 1 as emulsion active ingredients, 40 parts of dimethylacetamide, 40 parts of xylene, and 5 parts of polyoxyethylene alkyl allyl ether were mixed and mixed uniformly.
An emulsion containing 15 active ingredients was obtained.

When using, dilute with water to the specified concentration and spray.

Since the novel heterocyclic compound of general formula I has excellent herbicidal activity, it is suitable for controlling weeds growing in fields, orchards, non-agricultural lands, etc. Weeds can also be controlled by spraying this active compound onto the stems and leaves of growing weeds.

The dosage of this compound is regulated and the application rate is 1 per hectare.
-10k17, it can be used as a selective herbicide in fields where corn, wheat, barley, sugar cane, soybean, peanuts, sunflowers, potatoes, cotton, or fruit trees are cultivated. It can also be applied as a non-selective herbicide by increasing the application rate.

The compounds of the present invention can be used, for example, to control the following weeds: That is, dicotyledonous plants such as Stellaria media, Shiroza (
Chenopodium), Sagima
japonica), Chonopodiu
mficifolium), great dog (Polygon)
um nodosum), superhy (Portula
ceoleraeea), shepherd's purse (Capsella
bursapastoris)
epidium virginicum), Porippa 1ndica, Tanetsuke/<su(
CardamineHexuosa), Ichibi (Abu
tilon avicennae), 'Sida 5pinosa, crane/< morning glory (Ipomoea purpurea), 'Seneci.

Sonchus vulgaris), Sonchus vulgaris
asper), Bidens
frondosa), Ambrosia a
rtemisiaefo'1ia), broom daisy (As
ter gul)uljtus), Hotokenoza (Lam
ium amplexicavle), Katano'i
(Oxalis cornicolate).

Amaranthus retroflex
us), Vicia aativa
), Galiumspurium, Solanum nigrum % Datura stramonium
etc./Poaceae plants, such as P. oaa (p Oaa
nnua).

Alopeculus aequa
lis), Digitalia adsen
dens), Ohishino' (Eleusineindi)
ca), Setaria viridj
s), Echinochlor crus-
galli), Agropyron ts
Lo 1 i
umporenne), dog wheat (Bromus ca.
tharticos), oat (Avena ta)
tua), Po lypogon Hige
gaweri), Panicum di
chotom-iflorom), Cyperaceae weeds, such as Cyperu3 m1cro
iria), Kokoji Megayari(C)'perus
1ria)-Cusus+” (Carex rugata)
)etc.

The compounds of the present invention have excellent herbicidal efficacy against a wide range of weeds as described above, and particularly when sprayed on the foliage and foliage surfaces of plants at the beginning of their emergence, extremely high control effects can be obtained.

In order to demonstrate the herbicidal effect of the herbicide according to the present invention, some representative test examples will be given and explained in more detail.

Test example Foliar contact treatment (Foliar 5pray treat
(ment) (herbicidal effect on plants when the surface area is 100 crn2) Filled with K volcanic ash soil, Digitaria sanguinalis
), Echinochloa crus-g
Polygonum y
lodosum), Amaranthus
retro-flexu8), Tumo C1-r 7 (Z
ea mays), wheat (Triticum aes)
tivum), Phaseolusradii
Atus) seeds are sown, covered with about 1 crn of soil and placed in a greenhouse. When the weeds have 1 to 2 leaves, a hydrating agent of the compound of the present invention is applied in an amount equivalent to plOkg per 1 hectare. was diluted with water equivalent to 1000'll/ha and sprayed using a sprayer. Test Example 1 10 days after spraying the chemical
The survey was conducted using the same criteria as the above, and was expressed using a 6-level index. The test results are shown in Table 2.

Table 2 Stem and leaf treatment Applicant: Showa Denko Co., Ltd. Agent Kikuchi Sei - R9

Claims (1)

[Claims] 1) General formula (where X is 0.S, NH; Y is halodane; n is 0-2
an integer; R represents alkyl, acyl, carbamoyl, sulfonyl, alkoxycaryl or an alkali metal. ) A novel heterocyclic compound represented by 2) General formula (where, X is 0, 8, NH: Y is /%1lff
n is an integer of θ to 2; R represents alkyl, acyl, carbamoyl, sulfonyl, alkoxycarbonyl, or an alkali metal. ) A herbicide containing a novel heterocyclic compound as an active ingredient.