JPH05140155A - Benzoxazinyl tetrahydroquinazolinone derivative and herbicide containing it as an active ingredient - Google Patents

Abstract

(57) [Summary] (Corrected) [Constitution] The following formula [In the formula, R ¹ represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a benzyl group, a lower haloalkyl group or a lower alkoxy lower alkyl group, and R ² represents a hydrogen atom or a methyl group. ] The benzoxazinyl tetrahydroquinazolinone derivative shown by these. [Effect] The above compounds have excellent herbicidal activity against various weeds that are a problem in soil treatment and foliage treatment of upland fields, and flooding treatment of paddy fields, and have excellent selectivity between major crops and weeds. Therefore, it can be used as an active ingredient of a herbicide.

Description

Detailed Description of the Invention

[0001]

OBJECT OF THE INVENTION The present invention relates to a novel benzoxazinyltetrahydroquinazolinone derivative and a herbicide containing it as an active ingredient.

[0002]

The present invention has the general formula

[Chemical 2] [In the formula, R ¹ represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a benzyl group, a lower haloalkyl group or a lower alkoxy lower alkyl group, and R ² represents a hydrogen atom or a methyl group. ] It is related with the benzoxazinyl tetrahydroquinazolinone derivative shown by these (henceforth compound compound), and the herbicide which makes it an active ingredient.

The compounds of the present invention have excellent herbicidal efficacy,
It also shows excellent selectivity between crops and weeds. That is, the compound of the present invention, in the foliage treatment and soil treatment of upland,
Various weeds in question, for example, buckwheat vine, sanaetade, purslane, chickweed, white azalea, aogate, radish, velvetleaf, nazna, horned hazel,
Ebisugusa, hibiscus, American stag deer, field pansy, Yamgra, American morning glory, Malaga morning glory, Convolvulus vulgaris, Anopheles lanceolata, Pokemonosa, White-necked morning glory, Prunus perforatum, Steller's goldenrod, Cornflower, Cornflower, Cornflower, Cornflower Broad-leaved weeds, millet, barnyardgrass, green foxtail, sedgegrass, bluegrass, bluegrass, oat, oats, oats, syringa sorghum, rye barley, weeds of weeds of the family Oleaceae, such as grasshoppers, ginkgo biloba, Achinoe grass, and grasshoppers
It has herbicidal activity against Cyperaceae weeds such as Coccinella communis and the like, and the compound of the present invention does not show any phytotoxicity which is a problem to major crops such as corn, wheat, rice, soybean, cotton and sugar beet.

Further, the compound of the present invention can be used for various kinds of weeds that are problematic in the treatment of water in paddy fields, for example, weeds such as gramineous grasses, broad-leaved weeds such as Azena, Kishigusa and Mizohakobe; It has herbicidal activity against Cyperaceae weeds, eels and the like, and does not show any harmful phytotoxicity to rice.

The compounds of the present invention have the general formula

[Chemical 3] [In the formula, R ² has the same meaning as described above. And a compound represented by the general formula R ¹ -X [I] [wherein, X represents a chlorine atom, a bromine atom, a tosyloxy group or a mesyloxy group, and R ¹ has the same meaning as described above. ] It can manufacture by making it react with the compound shown by these.

This reaction is usually carried out without solvent or in a solvent,
It is carried out in the presence of a base, and the reaction temperature range is 0 to 100.
The temperature and the reaction time are in the range of 1 to 10 hours, and the amount of the reagent to be used in the reaction is 1.0 to 1.5 equivalents of the compound [I] and 1.0 to 1.5 equivalents of the base with respect to 1 equivalent of the compound shown in Chemical formula 3. Is.

Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, diisopropyl ether, dioxane, tetrahydrofuran and the like.
Examples thereof include ethers such as diethylene glycol dimethyl ether, nitriles such as acetonitrile and isobutyronitrile, acid amides such as formamide, N, N-dimethylformamide and acetamide, sulfur compounds such as dimethylsulfoxide and sulfolane, or a mixture thereof.

Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydride, and alkali metal alkoxides such as sodium methoxide and sodium ethoxide.

After completion of the reaction, the reaction solution is poured into water and subjected to usual post-treatments such as extraction with an organic solvent and concentration, and if necessary,
The desired compound of the present invention can be obtained by purification by operations such as chromatography, distillation and recrystallization.

It should be noted that some of the compounds of the present invention have optical isomers derived from an asymmetric carbon, and these optical isomers are also included in the present invention.

Next, a method for producing the compound represented by Chemical formula 3, which is a starting compound for the compound of the present invention, will be explained. The compound shown in Chemical formula 3 can be produced according to the route shown in Chemical formula 4.

[0012]

[Chemical 4] [In the formula, R ³ represents a lower alkyl group, and R ² has the same meaning as described above. ]

Compound [III] can be produced by reacting compound [II] with 1.0 to 3 equivalents of nitric acid per 1 equivalent of compound [II] at -10 to 20 ° C.
Next, 1.0 to 1.5 equivalents of the compound [III] and 1.0 to 2 equivalents of glycolic acid ester per 1 equivalent of the compound [III] are added.
Compound [IV] can be produced by reacting at 50 to 200 ° C. in the presence of an equivalent amount of potassium fluoride. Next, the compound [IV] can be reduced and ring-closed by using 3.0 to 10 equivalents of iron per 1 equivalent of the compound [IV] in the presence of an acid such as acetic acid to produce the compound represented by Chemical formula 3. it can.

Among the compounds [II], compounds in which R ² is a hydrogen atom are

[Chemical 5] It can be produced by reacting the compound represented by with Raney nickel for desulfurization. Among the compounds [II], the compound in which R ² is a methyl group is obtained by ring-opening the above compound in which R ² is a hydrogen atom using a nucleophile such as a secondary amine, and then condensation with acetyl chloride and ring closure. It can be manufactured by

When the compound of the present invention is used as an active ingredient of a herbicide, it is usually mixed with a solid carrier, a liquid carrier, a surfactant or other auxiliaries for formulation to prepare an emulsion, a wettable powder, a suspension,
Formulated in granules, wettable granules, etc. These formulations contain the compound of the present invention as an active ingredient in a weight ratio of 0.04 to 80%, preferably 0.06 to 70%.

As solid carriers, kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, walnut shell powder,
Examples thereof include fine powders or granules of urea, ammonium sulfate, synthetic hydrous silicon oxide and the like, and liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol and cellosolve, acetone and cyclohexanone. , Ketones such as isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, N, N-dimethylformamide, acetonitrile, water and the like.

Surfactants used for emulsification, dispersion, wet spreading, etc. include alkyl sulfate ester salts, alkyl sulfonates, alkyl aryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphates. Anionic surfactants such as ester salts, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. Is mentioned.

Other auxiliaries for formulation include lignin sulfonate, alginate, polyvinyl alcohol,
Examples include gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate) and the like.

The compound of the present invention can be used as an active ingredient of a herbicide for paddy fields, uplands, orchards, pastures, lawns, forests, non-agricultural lands and the like. The compound of the present invention is usually formulated and subjected to soil treatment, foliar treatment or flooding treatment before or after emergence of weeds. The soil treatment includes a soil surface treatment, a soil admixture treatment, and the like, and the foliage treatment includes a treatment from above the plant body and a local treatment such as treatment of only the weeds so as not to adhere to the crop.

When the compound of the present invention is used as an active ingredient of a herbicide, the amount to be treated varies depending on the weather conditions, formulation form, treatment time, method, place, target weeds, target crops, etc., but is usually 0.04 per 1 are. g to 80 g, preferably 0.08 g to 40 g, and emulsions, wettable powders, suspending agents, etc., usually have a predetermined amount of 1 liter to 10 liters per are.
It is diluted with liters of water (if necessary, an auxiliary agent such as a spreading agent is added) and treated, and granules and the like are generally treated without being diluted. Examples of the spreading agent include polyoxyethylene resin acid (ester), lignin sulfonate, abietic acid salt, dinaphthylmethane disulfonate, and paraffin in addition to the above-mentioned surfactant.

Further, when used in combination with other herbicides, the herbicidal effect can be expected to be enhanced. Furthermore, it can be used by mixing with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners and the like.

The compound of the present invention can also be used as an active ingredient of a defoliant for crops such as cotton and potato, and a harvesting aid such as a desiccant.

Hereinafter, the present invention will be described in more detail with reference to production examples, formulation examples and test examples, but the present invention is not limited to these examples. First, production examples of the compound of the present invention will be shown.

Production Example 1 (Production of Compound (19)) 3- (7-Fluoro-3-oxo-1,4-benzoxazin-6-yl) -5,6,7,8-tetrahydroquinazoline-4- On 0.5g, anhydrous potassium carbonate (0.3
A mixture of g), dimethylformamide (10 ml) and propargyl bromide (0.21 g) was stirred at room temperature for 3 hours. The reaction solution was poured into water and extracted with ethyl acetate. The extract was concentrated under reduced pressure to give 3- (4-propargyl-7-fluoro-3-oxo-1,4-benzoxazin-6-yl) -5,6,6.
0.22 g of 7,8-tetrahydroquinazolin-4-one was obtained.

Next, some of the compounds of the present invention produced according to this production method are shown in Tables 1 and 2.

[0026]

[Table 1]

[0027]

[Table 2]

Next, production examples of the compound represented by Chemical formula 3, which is the starting compound for the compound of the present invention, will be shown.

Production Example 2 3- (2,4-difluorophenyl) -5,6,7,8
-Tetrahydroquinazolin-4-one [mp162-1
63 ° C] (4.6g) with d = 1.50 nitric acid (0.9g), concentrated sulfuric acid
(3.0 g) was added, and the mixture was reacted at 0 to 5 ° C for 3 hours.
After completion of the reaction, the reaction solution was poured into water, and the generated crystals were collected by filtration. After washing with water and drying, 3- (2,4-difluoro-5-nitrophenyl) -5,6,7,8-tetrahydroquinazolin-4-one [mp 207.0 ° C] (3.98 g) was obtained.

The above 3- (2,4-difluoro-5-nitrophenyl) -5,6,7,8-tetrahydroquinazolin-4-one (3.9 g), potassium fluoride (2.2 g),
1,4-dioxane (50 ml), butyl glycolate
The mixture of (3.9 g) was heated under reflux for 10 hours. After completion of the reaction, water was added and the mixture was extracted with ethyl acetate, dried and concentrated. The residue (4.3g) contains the target compound 3 containing a small amount of butyl glycolate.
-(2-fluoro-4-butoxycarbonylmethoxy-
It was 5-nitrophenyl) -5,6,7,8-tetrahydroquinazolin-4-one. This crude product was subjected to the next step without purification.

Iron (3.5 g), water (3 ml), acetic acid (30 m
The suspension of l) is heated to 80-90 ° C, whereupon the crude 3
-(2-fluoro-4-butoxycarbonylmethoxy-
A solution of 5-nitrophenyl) -5,6,7,8-tetrahydroquinazolin-4-one (4.3 g) in 1,2-dichloroethane (30 ml) was added dropwise at the same temperature. After the mixture was vigorously stirred for 30 minutes after the dropping, excess iron powder was filtered off, and the filtrate was added to
-Extracted with dichloroethane. The extract was washed with water and saturated sodium bicarbonate water, dried, and concentrated. The residue was purified by silica gel column chromatography, 3- (7-fluoro-3-oxo-1,4-benzoxazin-6-yl) -5,6,7,8-tetrahydroquinazoline-4-.
On (1.3 g) was obtained. mp220-221 ℃

Next, formulation examples are shown. The compounds of the present invention are shown by the compound numbers in Tables 1 and 2. Parts are parts by weight.

Formulation Example 1 Compounds of the present invention (5), (15), (19), (23),
(29) 50 parts each, calcium lignin sulfonate 3
Parts, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are well pulverized and mixed to obtain wettable powders. Formulation Example 2 Compounds of the present invention (5), (15), (19), (23),
(29) 10 parts of each, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzene sulfonate, and 70 parts of xylene are thoroughly mixed to obtain an emulsion. Formulation Example 3 Compounds of the present invention (5), (15), (19), (23),
(29) 2 parts of each, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are well pulverized and mixed, water is added and kneaded well, and then granulated and dried. Obtain each granule. Formulation Example 4 Compounds of the present invention (5), (15), (19), (23),
(29) 25 parts of each, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC, and 69 parts of water are mixed and wet-milled until the particle size becomes 5 microns or less to obtain each suspension agent.

Next, it is shown in Test Examples that the compound of the present invention is useful as an active ingredient of a herbicide. The compounds of the present invention are shown by the compound numbers in Tables 1 and 2. In addition, the herbicidal efficacy and phytotoxicity were evaluated using the test plants (weeds and crops) at the time of the survey.
"0" indicates that there is no or almost no difference in the emergence and growth state of untreated plants, and "5" indicates that the test plant is completely dead or that the emergence or growth is completely suppressed. , Divided into 6 stages from 0 to 5,
Shown as 0, 1, 2, 3, 4, 5.

Test Example 1 Field soil surface treatment test Field soil was packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and seeds of millet, oat, malaba morning glory, and velvetleaf were sown and covered with soil. The test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount of the compound was diluted with water equivalent to 10 liters per are, and the soil surface was treated with a small sprayer.
After the treatment, it was grown in a greenhouse for 20 days, and the herbicidal effect was investigated.
The results are shown in Table 3.

[0036]

[Table 3]

Test Example 2 Field Stem / Leaf Treatment Test Field soil was filled in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and seeds of millet, Malaga morning glory, Japanese radish, and hibiscus were sown and grown in a greenhouse for 10 days. Thereafter, the test compound was made into an emulsion in accordance with Formulation Example 2 and the predetermined amount thereof was adjusted to 1
It was diluted with water containing a spreader equivalent to 10 liters per are, and foliage treatment was performed from above the plant with a small sprayer. After the treatment, it was grown in a greenhouse for 20 days, and the herbicidal effect was investigated. The results are shown in Table 4.

[0038]

[Table 4]

Test Example 3 Paddy Flooding Treatment Test Paddy soil was packed in a cylindrical plastic pot having a diameter of 8 cm and a depth of 12 cm, and seeds of Taenia muscaria were mixed to a depth of 1 to 2 cm. After flooding to make paddy fields, rice at the two-leaf stage was transplanted and grown in a greenhouse. Six days later (the initial stage of the development of each weed), the test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with 5 ml of water and treated on the water surface.
After the treatment, the plants were grown in a greenhouse for 20 days, and herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 5.

[0040]

[Table 5]

[0041]

INDUSTRIAL APPLICABILITY The compound of the present invention has an excellent herbicidal activity against various weeds which are problematic in the soil treatment and foliage treatment of upland fields, and the flooding treatment of paddy fields, and is excellent between major crops and weeds. Since it shows selectivity, it can be used for various purposes as an active ingredient of a herbicide.

Front page continued (72) Inventor Shoji Sakaki 42-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd. (72) Shinsuke Ikushima 4-2-1 Takashi, Takarazuka, Hyogo Sumitomo Kagaku Industry Co., Ltd.

Claims (2)

[Claims] 1. A general formula: ## STR1 ## [In the formula, R ¹ represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a benzyl group, a lower haloalkyl group or a lower alkoxy lower alkyl group, and R ² represents a hydrogen atom or a methyl group. ] The benzoxazinyl tetrahydroquinazolinone derivative shown by these. 2. A herbicide containing the benzoxazinyltetrahydroquinazolinone derivative according to claim 1 as an active ingredient.