WO1988004652A1 - Heterocyclic compounds having triketo skeleton - Google Patents

Abstract

Compounds represented by general formula (I) (wherein R1 represents a hydrogen atom, a group of -D-r1 (wherein -D- represents -CO- or -SO2- and r1 represents a lower alkyl group or an optionally substituted phenyl group), an optionally substituted lower alkyl group, or a group of formula (II), wherein Y represents an oxygen or sulfur atom, and r2 and r3 each represents a lower alkyl group), A represents an optionally substituted methylene, ethylene or vinylene group, B represents an optionally substituted phenyl, naphthyl or 5- to 10-membered aromatic heterocyclic group containing an oxygen, sulfur or nitrogen atom, and -X- represents -O-, -S- or a group of formula (III) (wherein r12 represents a hydrogen atom or a lower alkyl group) or salts thereof, process for their preparation, and herbicides containing same as effective ingredients.

Description

 Details

 Complex compounds with triketone skeleton Technical field:

 The present invention relates to a new compound, a method for producing the compound, and a herbicide which contains the compound as an effective component. Background technology

 In the cultivation of agricultural and horticultural crops, many herbicides have been used for weed weeding, which has required a great deal of labor. It is safe to use because it has the potential to cause harm to crops, to cause harm to crops, to remain in the environment, to be contaminated, and to be effective. Drug development is underway. Disclosure of the invention:

 The purpose of the present invention is to produce a new complex compound in an industrially advantageous manner, to provide a wide selection range between crops and weeds, and to ensure a high effect. It is to provide herbicides with high safety.

 This invention is a general formula

X, 0

 A

OR, COB In the formula, R, hydrogen atom formula-D _ In the formula, D is - CO - or, - S ◦ ₂ - a, r ¹ is lower A Le key Le group or (C B gain down atom, a lower A Le key Le group was rather is replacement in two preparative port group ) It indicates a phenyl group. } Even if it is substituted with a lower alkoxycarbonyl group.

Υ ₂

Good lower alkyl group or formula -ρ- < ^0Γ , where Υ is oxygen source

'■ — — or ³ -represents a child or sulfur atom, and r ² and r ^{3 each} represent a lower alkyl group. ) Represents a group represented by

A represents a group represented by the formula--C-"n- O— {wherein, r ⁴ , r ³

 I I

r ⁵ r ⁷

r ⁶ and r ⁷ are each a hydrogen atom, a lower alkyl group, or (substituted by a halogen atom or a lower alkyl group). II represents a benzyl group, and II represents 0 or 1. However then, n-out is 1 bet is r ⁴ or r ⁵ is r ⁶ is a double bond or in Tsu name in to One had a r ⁷ Yo but it may also form a璟. }

B represents a {nitrogen atom, a dinitro group, a cyano group, (which may be substituted with a halogen atom or a phenyl group); a lower alkyl group; group, a lower § Le key Le mosquitoes Le ball two group, a lower A Le co key imposes Le ball two group, or the formula - E - r ⁸ (wherein one E - is

Γ ⁹

One 0 -, - -S (0) m - (m: 0, 1, 2) or one ώ one (r ^9: a hydrogen atom, a lower § Le key Le group), and the gamma ⁸ (c b gain down A lower alkyl group, which may be substituted with an atom or a phenyl group, or a (substituted with a halogen atom or a halogen atom). Or it may be substituted with a lower alkyl group.) Full two Norre group, wherein one N rather ^Γ "1 0 1 I: Water atom also rather lower A Le key Le group) rather also groups that will be I table in an oxygen atom, a sulfur atom or nitrogen And represents a 5- to 10-membered heterocyclic group which represents an atom.) May be replaced by a group represented by the formula: (a phenyl group, a naphthyl group or Is a 5- to 0-membered aromatic heterocyclic group containing an oxygen atom, a sulfur atom or a nitrogen atom), and X is

— 0 —, — S — or — — (wherein, r ¹² represents a hydrogen atom or a lower alkyl group). Or a salt thereof, a method for producing the compound, and a herbicide containing the compound as an active ingredient.

Best mode for carrying out the invention: The compound of the present invention can be produced by the following method

① If n = 0, H;

0

 M-X-C-COCHCOB

r ⁷ COOQ

 OH COB

 ] CI] '

(In the formula, M represents a hydrogen atom or a protecting group for the group represented by XH, and Q represents a hydrogen atom or a lower alkyl group.) The reaction is carried out in a solvent, a base or an acid. In the presence of the solvent, the reaction is carried out at a pressure of −10 to a boiling point of the solvent to be used for 30 minutes, and then for 10 hours. When M is other than a hydrogen atom, the protecting group represented by M includes acetylene groups such as acetylene groups, benzyl groups, methoxymethylene groups, Usual protecting groups such as a 0H group and an SH group can be used such as a transhydryl group. As a solvent, an organic solvent such as benzene, tosoleene, ΤF, or phenolic alcohol, or water can be used. As bases or acids, salts such as sodium hydride, potassium carbonate, sodium hydride, decylamine, viridine and the like »P—toluene The raw material compound represented by the general formula CII] in which an acid such as enzulonic acid or sulfuric acid can be used can be produced, for example, according to the following reaction formula. Thus, it is also possible to carry out the method of the invention without isolation.

BCOCHz COOQ + M-X-C-COC £

[IV]

 -> -X-C-COCHCOB

r ⁷ COOQ

 CH]

② When n 1, R _t = Η;

B

B

 ΟΗ

[V] [VI] [In the formula, Z represents a halogen atom, a hydroxy group, a lower alkoxy group or 10- (acid anhydride). The reaction is carried out in the presence of a salt group in the presence of

The compound represented by [] is obtained and isolated.

 O CO B

 After that, or by using the transfer agent without isolation. As the solvent, a solvent such as THF, benzene, tonolene, ethylenol, viridine, water, or the like can be used. Examples of the base include pyridin, tritienoleamine, sodium hydroxide, and phenolic acid.

 '·

 Dess, hydrogenated sodium, potassium carbonate, small lithium, etc. can be used. The reaction that causes the transfer test to work is also in organic solvents such as Benzene, Toluene, Cloth holme, THF, Etherenol, and Dioxane. Use a solvent-free solution. Examples of the transfer test include aluminum chloride, zinc chloride, zinc tetrachloride, tetrasodium tetrachloride, boron trifluoride ethereolone, and the like. Cyanides such as sethocyanhydrin, methansulfonates, concentrated sulfuric acid, and N, N-dimethyl-amino-bizines Can be used. All reaction temperatures are up to the boiling point of the solvent used.

③ In the case of ί? And ≠ H; the reaction is represented by the general formula [1] 'or [1] "in an organic solvent. The reaction is carried out by reacting the compound to be reacted with a corresponding halogenated compound, ester, or the like.

 The salt of the compound of the present invention reacts the compound represented by [I] 'or [I] "with the corresponding salt in an organic solvent or an aqueous solution. Thus, the structure of the obtained salt is i

B

B

(Formulas Φ, R, and 'represent an alkali metal, an alkaline earth metal, a transition metal, an ammonium, and the like, and k represents 1, 2, 3,...) Is

の キ レ ー ト .構 造等 が考 え ら れ る 。

The structure, etc. of the chelate can be considered.

Regardless of the reaction performed in any of the methods (1), (2), and (3), the target product can be obtained in good yield by performing the usual post-treatment after the reaction. . The structure of the compound of the present invention was determined based on the data from IR, NMR, MASS, etc. The compounds of the present invention represented by the general formula [I] have the following tautomeric forms, but the present invention is based on these tautomeric forms. It is a thing.

さ ら に 一 般式 [ v ] で 表 わ さ れ る 原 料 化 合物 に も 同 様 の 異 性 休 が存在 し 、 従 っ て 一 般 式 [ VE ] で 表 わ さ れ る 中 間 体 も 下記 の 2 種 類 が考 え ら れ る 。 C0 B

In addition, the raw material compound represented by the general formula [v] has a similar heterologous rest, and accordingly, the intermediate compound represented by the general formula [VE] The following two types are also considered. C0 B

次 に 実 施 例 を 举 げ 本 発 明 化 合 物 を 更 に 詳 細 に 説 明 す る 実 施 例 1

Next, the present invention will be described in further detail with reference to Examples 1 and 2.

3 — (2, 4 — hood) 1 2, 5 — 1-hydro 4 — 1-hydroxide 5 — 1- 2 (Compound No. 6)

4 ... Acetyl ratio 2-(2,4-Cyclopentabenzene)-3-Methyl oxopentanoate 2.4 g Was added to a 5% sodium hydroxide solution (NaOH 0.51 g) under ice-cooling, and the mixture was allowed to stand at room temperature for 2 hours. After the reaction mixture was washed with ether, the alkaline layer was carefully acidified with 2N-hydrochloric acid under ice-cooling, and the liberated oily product was extracted with sulfuric acid. Was After drying over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was recrystallized from ethanol to obtain 0.4 g of the intended product. m. p. 1 2 4. ~ 1 2 5 'C Example 2

3 (2 dichlorobenzene) 1 4 Hydroxy 1 6-Methyl 1 2-Pyrone ( ^: Compound No. 30)

ヒ ド ロ キ ジ、 一 6 — メ チ ノレ 一 2 — ビ ロ ン 5 g と 2 ，

Hydrology, one 6 — methylone 2 — virone 5 g and two,

4 — Dissolve 8.3 g of dichlorobenzene benzoyl chloride guide in 70 mL of THF, apply 3.2 g of pyridiline, and apply for 1 'hour. The heat returned. After cooling the reaction solution, it was poured into ice water (300) and extracted with ethyl acetate (300). The acetic acid E Ji Le layer with 1 N hydrochloric acid 1 0 0 wash, in _{1 0% N a z t 0} 3 water soluble liquid 2 0 0 In the next doctor wash

 , ノ.

 Then, the dehydrating solvent was depressurized and distilled off using sodium hydrogen sulfate.

 Dissolve the reactants in 50 tetrachloroethane.10.

6 g of anhydrous sodium chloride was added, and the mixture was heated and refluxed for 2 hours while stirring. After the reaction, the mixture was poured into ice water (500) and extracted with ethyl acetate (500). The peroxidic acid layer was washed three times with 1N hydrochloric acid 300 and extracted twice with 0.5N Na0H aqueous solution 300. The alkaline layer is made p112 with concentrated hydrochloric acid, extracted with methylene chloride 300, dewatered with magnesium sulfate-free magnesium, and the solvent is distilled under reduced pressure. -I left. -The obtained crude product was purified by a silica gel, a gel, and a mat graph to obtain 6.5 g of a target substance.

m. p. 1 0 5 1 0 7

Example 3

(2, 4 ジ 口 ソ) 4-(4-Methyl benzoyloxy) virone (Compound No. 31):

COCjg

3 — (2, 4 — cyclo σ benzoyl) 1 4 — hydroxy

 9

1 6 1 Methyl 2-Pyrone 1 g and 3.4-Methyl benzoyl

 C

0.5 g of chloride was dissolved in 20 T fl F, and 0.26 g of viridine was added, followed by heating under reflux for 1 hour. The reaction mixture was poured into 100 ml of ice water, and the extracted organic layer was extracted with 100 ml of ethyl acetate. The organic layer was washed with 10% Na ₂ C 03, washed with anhydrous magnesium sulfate. After dewatering with, the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel chromatography to obtain 0.9 g of the intended product. m. p. 9 1 Example 4

3 — (2, 4 — Venom's benzoin) 4 Hydroxy I 1, 6 — Dimethyl hydrido pyridine 1 2 — ON (Compound No. 5 4) _:

ヒ ド ロ キ シ 1 ， 6 ジ メ チ ノレ ジ ヒ ド 口 ビ リ ジ ン

Hydrogen 1, 6 Dimethyl resin

2—Dissolve 3.0 g of on in Benzene 30 and add 1.

9 g, 2, 4-Add 4-g of cyclohexene benzoyl chloride under ice-water cooling, return to room temperature, and react for 2 hours. After the reaction, the reaction solution was washed with an aqueous solution of sodium bicarbonate and a saturated saline solution in that order. Further 1

After washing with N-hydrochloric acid and saturated brine, the organic layer was dried with magnesium sulfate-free, and the solvent was distilled off under reduced pressure to obtain 6.4 g of an intermediate. . Dissolve 3 g of this intermediate in 1,1,2,2—tetrachlorethane 30 and add 1.6 g of anhydrous sodium chloride medium. And refluxed for 3 hours. After cooling the reaction mixture, it was poured into ice-cooled diluted hydrochloric acid, and the organic layer was separated. After the organic layer was extracted with a 5% aqueous solution of sodium hydroxide, the aluminum layer was acidified with 2N-hydrochloric acid and extracted with ethyl acetate. After drying with anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and purified by silica gel chromatography to obtain 0.2 g of the intended product. Was m.p.l 7 4 ° ~ 1 7 5

Example 5

 (2 dichlorobenso'inole) Hydroxymethine2,5 dihydrofuranone (compound number 5 · -3)

2 , 4 — ジ ク ロ 口 べ ン ゾ ィ ノレ 酢 酸 メ チ ノレ 5. 0 g を ベ ン ゼ ン 5 0 m£ に f容 解 し 、 等 モ ノレ の マ グ ネ シ ウ ム ェ チ ラ 一 卜

2, 4 — Dichloro mouth benzoyl benzoate 5.0 g of methyl acetate is dissolved in 50 ml of benzene f, and the magnole magnesila One part

(2.3 g) was added at room temperature, and the mixture was stirred at the same temperature for 1 hour. To this solution, 3.1 g of L-'acetoxypropionyl chloride was added under ice-cooling. After stirring at room temperature for 3 hours, the reaction mixture was poured into ice-cooled diluted hydrochloric acid, and the benzene layer was separated. The organic layer was washed with saturated saline, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 7.0 g of a crude intermediate. This was added to a 5% aqueous sodium hydroxide solution under ice-cooling, and allowed to stand at room temperature for 12 hours. The reaction solution was washed with a pot, the acid layer was carefully acidified with 2N monohydrochloric acid, and the crystals which eluted were filtered out to obtain the intended product 0.8. m. p. 24 0 'C or more.

Table 1 shows typical examples of the compounds of the present invention produced in the same manner as in the above Examples.

Table 1

' Structural formula

Le ¾n Afm

数 番 Ύ。 〔 〕 て Buried

Number Ύ. 〔 〕 hand

 OR, COB

 R. A B X

1 H — CH ₂ ― s [80 81]

2 〃 〃 〃 (155.5

 loo.oj

CH ₃ ^S

 3 1/2 Cu-Q> 〃 250 'C shame

 -CH-

4 1/2 Mg 250 'Cl> ± 160]

5 1/2 Ca ft 〃 (158

 Ti

6 H C £ s (124 125)

7 〃 〃-0>-CH ₃ [63.5 ~ 65]

8 〃 〃 〔45 46〕 £

 9 C £ [91 93]]

10 〃 § -§ -N0z 〃 (209 211

 jf ^ f

11 〃 -CIIz-〃 (138 139)

CH ₃

 12 (79 to 80)

-ιι- 1 Table

c

 A B X

 C ¾

 H (96 97)

 Zi

C £ CH ₃

 C £ (105.5

CH ₃

-CH- (55 56) 0CH ₃

/ rn "' ⁵ 1.6234

CH ₃

-^) -CH ₃ (90 91)

(136 137)

CH ₃

 C… C £

 -^) -C £ (118 120)

CzHs

 -CH- Good C £ (102 104)

CH ₃

 -cn- move

(112 114)

0CII ₃

-^) -N0 ₂ (211 212)

CIf ₃

(66 67) CH3 1 Table

' Structural formula

/ μm ¾π ΐJ ¾ fe «A number c]

 R i A B X

 NO-

25 H s (128 129)

 II

II II o 1 U2,, Π3

 Jiichi

 26 〃

 in ¾ -¾ 〃 C134 136)

S

 27 〃 〃 // C152 153)

28 〃 /,

Q 5 153〕

Q 5 153)

F

, / CH ₃

 29 F // αΐ2 113)

 — CH—

30 ,, a 0 Q05 则

31 -CO PU CH ₃ / // [91 93]

32 -S0 ₂ -@-CH ₃ Q26 128)

33 H // [56 58]

34 -SOz- ^ CHa 〃 〃 [94 95]

35 H 〃 〃 Viewing

 S

CH ₃ * 3

36-P- (0C _z H ₅ ) ₂ 〃

-CH = C- (X)

1 Table

1 表 （っ き）

1 Table

1 表 （つ き） 構 造 式 化合物 物理 t旦数 番 可 〔 〕 ¾*c

1 Table (Continued) Structural formula Compound Physics Number of times possible [] ¾ * c

 COB

A B. X

N0 ₂ '¾

CH ₃

84 H-O ^ N0 ₂ 0 240'Clilh

 -CH = C- (X)

 NOz

85 tr - O N0 ₂ [218 220]

86 it [196 198]

 Ω

 u

N0 ₂

87 \ -¾f (o-SC _z H ₅ [11 116]

N0 ₂

88 tr -¾> -so ₂ cii ₃ (204 205)

N0 ₂ ^ 0CH ₃

Cli ₃

 89 (203 205)

 -CH = C- (X)

N0 _Z

90-O -S0 ₂ CHzC £ 〃 (145 148)

CII ₃ S

91 〃, CF ₃ (168 170)

C1I ₃ 0 ₂ S.

 92 〔168〜 丄 70〕

NOz

93 -S-CF ₃ (185 195)

94 (17 175)

Cl! ₃ CH ₃

95 〃-OhS0 _z CH ₃ (190 192) i table

1 表 （つ き）

1 table

1 表 （っ き）

1 Table

第 1 表 （っ き)

Table 1

(x): X «H job ι Φ x x, A and χ and © ^ imaginary ^

* 1-N M R (C D C 3) δ: 1.70 (d, 311), 2, 57 (s, 3H)

4.27 (ς, 1 ID, 7.2583 (each d. 4H in total)

10-20 (.brs.1H)

* 2 ^ -NMR CDC £ ₃ ) 6: 1.34 ", 911), 6.16 (s, 1H) 7.26, 7.38, 7.50 (each d, 3H), 17.40 ( s, 1 H)

 ,

* 3 ^ I-NMR (CD6 £ ₃ ) 6: 1, 32 (t, '6H), 2.34 (s, 3H) 4.18, (q, 4H), 6.50 ", 1! 1), 7.38, 7.44, 7.64 (each d, 3H)

* 4 ll-NMR (CDC _g ₃ ) ^: 2.46 (s, 311), 7.20 (s, 1H)

7.4 to 8.4 (m, 12H) * 5 ^] H-N MR (CDC ί ₃ ) δ: 1.38 (d, 611), 2.52 (s, 3H) 3.50 (m, 1 H), 6.06 (s, 1 H), 7.08, 7-42 (each d,

2H), 17.40 (s, 1 H) * 6-NMR (CDC jg ₃ ) <J: 1.55 (s, 6 H), 3.00 (s, 2H) 7.22 (d, 1 ID , 7.66 (dd, 1 H), 8.18, (d, 1 H), 17.2 (brs, 1 H)

twenty five

 The herbicide of the present invention contains one or more of the compounds represented by the above general formula [I] as an active ingredient, and has a form similar to that of ordinary and pesticides. . That is, the active ingredient compound is generally used in the form of a wettable powder, an emulsion, a granule, a water solvent, a free thorn, or the like, which is mixed with an appropriate amount of a carrier and used. . Examples of solid carriers include tanolek, whey carbon, bentonite, clay, cascade soil, and the like. Examples of solid carriers include liquid carriers. , Water, vinyl, benzene, xylene, kerosene, mineral oil, xpi, xixan xanon, dimethylmethyl Amides etc. are used. Surfactants can be added if necessary to obtain a uniform and stable form in these preparations.

 The concentration of the active ingredient in the herbicide of the present invention may vary depending on the form of the preparation as described above. For example, in the case of a wettable powder, the concentration of the active ingredient is 5%. ~ 70%, preferably 1 ~ 30%: 3 ~ 70% for milk, preferably 5 ~ 20%: 0 ~ 0 for granules. Concentrations of 0.1 to 3%, preferably 0.05 to 10% are used.

The wettable powder and milky powder thus obtained are diluted to a predetermined concentration with water to prepare a suspension or an emulsion, and the granules are used as they are before germination of the weeds. After germination, the soil is sprayed or mixed. In actual application of the herbicide of the present invention, an appropriate amount of 1 g or more of the active ingredient per 10 ares is applied. The present herbicide can also be used in combination with known fungicides, insecticides, herbicides, herbicides, plant growth regulators and the like. In particular, the use of a mixture with a herbicide not only reduces the amount of used medicine and saves labor, but also enhances the synergy of the combined medicine. The effect can also be expected. In that case ,

Combinations with several known herbicides are also possible. Suitable drugs to be used in combination with the herbicide of the present invention include van carb, molynate, MY-93 [S — (2, 2 — Dimethyl benzone) 1 — Carbamate herbicide such as biperidine resin, etc., and thiocarbamate herbicide Acid amide herbicides such as butacronoline, phlecinoleno, mefenacet, etc., chromatoxinole, and binox And other triadine herbicides such as atrazine and cyanadine, chlorsulfuron, and snorreho. Snorre honyl and herbicides such as methyluron and methylenol, and herbicides such as MCP and MCPB. Diclohop 'Phase of methisoles, etc.'>'Nokishi fenoxyprobionic herbicides, full-azihop butyr' Etc., such as viscous plastics, lipoic acid-based herbicides, venso'-yl-broch ' Benzo noreaminoff, σ-bionic acid herbicides such as echinoles, and others, such as Viverohos, Dymron, and Ventason ' , Difenso 'Coat, Nablo Anilide, HW-52 (4-2-, 3'-Cyclonorre 2 Ride), KNW — [1 — (3 — 1-5, 1-, 2, 4--triazole-1 3-carboxamido), with a kick-out rack (37) — Dichloro. 8 — Quinolin carbonic acid), and further to the mouth of the liquid, such as setoxime, anoxoxime-sodium, etc. Zeon herbicides are required. It is also possible to add planted ife oil and oil concentrates to these combinations. -Next, there are some examples of preparations related to the herbicide of the present invention, but the effective differentiation compounds, additives, and the ratio of addition can be changed in a wide range without being limited to only this example. Noh.

Example 6 wettable powder

 The compound of the present invention: 120 parts White carbon: 20 parts Keiso soil: 52 parts Alkylsulfuric acid Zoda: 8 parts-Mix uniformly, pulverize finely As a result, a wettable powder with an effective component of 20% was obtained.

Example 7 Emulsion

Compounds of the present invention 3 3 2 0 parts Kiren 5 5 parts Dimethylformamide 15 parts Polyethylene ethylene ester More than 10 parts Was mixed and dissolved to obtain an effective component. A 20% emulsion was obtained in Example 8. Compound number 1 4 5 parts Talk 40 parts Cle 38 parts Hentnite 10 parts Alkylsulfuric acid sodium 7 parts or more are evenly mixed and mixed. The granules were finely pulverized and granulated into 0.5 to 1.0 hidden particles to obtain granules having an effective component of 5%. Industrial applicability:,

 The following shows test examples on the effects of the herbicides of the present invention.

Test example 1 Paddy soil treatment test

 Fill the bottom of the 150 era box with paddy soil, sow seeds of Tamagayari, Omodaka and Hotarui, lightly cover the soil, The plants were transplanted, and one day (2 strains) of rice at the 2-3 leaf stage (2 strains) was transplanted. The next day after transplanting, a water depth of 23 cm was maintained. The grains were treated at a prescribed dose and grown in a greenhouse. Three weeks after the chemical treatment, the growth status of rice and each weed was surveyed according to the following criteria, and the survey criteria obtained the results shown in Table 2 were obtained.

 Weed killing rate JH number

 0%

 20 to 29%

 40 to 49% 4

6 0 to 6 9% 6 80 to 89% 8100% 10 or 3, -5, 7 and 9 are 0 and 2, 2 and 4 and 6, 6 and 8 and 8 and 10 respectively. Aboveground raw grass weight of untreated plots showing the value between the plots-Aboveground fresh grass weight of the treated plots

 Herbicide (%)-X 100 Above ground grass in untreated area

Table 2

実施例 2 茎 葉 散 布 処理

Example 2 Stem leaf spraying treatment

Fill the pot of 200 crf with soil, sow the seeds of akaza, ichibi, kyari, gusa and wheat on the surface layer, lightly cover the soil and then in the greenhouse It was grown in. When each weed grew to a height of 5 to 10 n, the milk of each test compound was adjusted by diluting it with water.

 , ',

 A chemical solution of 100 000 or 200 pm is applied to a small nebulizer at a ratio of 100 a to 100 a (100 a or 100 g of 100 a). And sprayed on the foliage of weeds. Three weeks later, weed growth was investigated according to the investigation criteria in Test Example 1, and the results are shown in Table 3. 3rd growth status

 Active ingredient

 Compound g / 10a Combination calibration force

30 200 0 10 10 10

37 200 0 10 10 10

38 200 0 10 9 10

39 200 0 10 9 10

86 200 3 10 10

88 200 2 10 10 10

91 200 0 10 10 10

92 200 0 10 10 10

93 200 3 10 10 10

95 .200 0 10 10 10

96 200 3 10 10 10

98 100 2 10 9 10

99 100 2 10 10 10

100 100 3 10 10 10

 109 100 0 10 10 10

 1 10 100 0 10 10 10

 1 15 100 3 10 10 10

Claims

 Request box General formula

[Wherein, is a hydrogen atom, formula 1 D-r «{wherein, 1 D — is — C 0 — or 1 S 0 _z丄, and r ¹ is a lower alkyl group or It may be replaced by a gen atom, a lower alkyl group or a nitro group.) A phenyl group. Even if it is substituted with a lower alkoxycarbonyl group.  Y II or A lower alkyl group or a formula ^{P_ <} _OT 3 (wherein, Y represents an oxygen atom or a sulfur atom, and r ² and r ^{3 each} represent a lower phenol group. ) A represents a group that cannot be represented by the formula C + C (wherein r ⁶ and I " ⁷ are each a hydrogen atom, a lower alkyl group, or a lower atom having a hydrogen atom, respectively. A phenyl group; n represents 0 or 1, provided that when n is 1, r ⁴ or When is it 2 May form a 蜇 bond or 璟 B represents a {p gen atom, a nitro group, a cyano group, a (halogen It may be substituted with an atom or a vinyl group.) Lower phenolic group, lower alkyl carbonyl group, lower alkoxy carbonyl group , Group, or the formula 1 E — r ⁸ (wherein, 1 E — is Γ ⁹ - 0 -, - S (0 ) m - (m: 0, 1, 2) or an N - _(Γ ^9: Water atom, lower §, Le key Le group) a, r ^S (C B gain down A lower alkylene group (which may be substituted with an atom or a phenyl group) or a (substituted with a halogen atom or a halogen atom) May be replaced by a lower alkyl group.) A vinyl group is represented by the formula: N ^{1 1} _u (r '°, r ^{11 1} : hydrogen atom or A lower alkyl group) or a 5- to 10-membered heterocyclic group containing an oxygen atom, a sulfur atom or a nitrogen atom.) ' (A 5- to 10-membered aromatic heterocyclic group containing a phenyl group, a naphthyl group or an oxygen atom, a sulfur atom or a nitrogen atom) ,-X- 1 ² A compound represented by f ′] which represents one 0 —, — S-or — N— (wherein, r ¹² represents a hydrogen atom or a lower alkyl group). Is its salt. 2. General formula r ⁶  I  M-X-C-CO-CHCOB r ⁷ COOQ [Wherein, r ⁶ and r ⁷ are each a hydrogen atom or a lower alkyl group. Alternatively, a phenyl group (which may be substituted with a halogen atom or a lower alkyl group) may be substituted with a halogen atom, a nitro group, A cyano group, which may be substituted with a halogenated Yasuko or a phenyl group, a lower alkyl group, a lower alkyl group, a non-alkyl group, a boninole group, lower A Le co key imposes Rubo group, or the formula - E - r ⁸ (wherein, '; single E - one 0 -, - S (0) m - (m: 0, 1, 2) or 1 N— (hydrogen atom-lower alkyl group), and r B (can be substituted with a c-halogen atom or a phenyl group). Lower alkyl groups, (lower alkyl groups which may be substituted with halo or halogen atoms)  .Ten Phenyl group, I 0 — Ku.  I I r ¹¹ represents a group represented by a hydrogen atom or a lower alkyl group) or a 5- to 10-membered heterocyclic group containing an oxygen atom, a sulfur atom or a nitrogen atom. . ) May be substituted with a group represented by the following formula) (a phenyl group, a naphthyl group, or an oxygen atom, a sulfur atom X is a 5- to 10-membered group containing a nitrogen atom) The aromatic heterocycle  1 2 ), — X 1 is 1 0 —, 1 S — or — Ν-(wherein, 12 represents a hydrogen atom or a lower alkyl group.) Μ represents a hydrogen atom or a protecting group for the group represented by XΗ, and Q represents a hydrogen atom or a lower alkyl group. A compound represented by the general formula: , X, 0 OH COB (In the formula, r ⁶ , r ⁷ , X and B have the same meanings as described above.) A method for producing a compound represented by the formula: 3. —General formula or Ma

[In the formula, rr ⁵ , r ⁶ , and r ^{7 each} represent a hydrogen atom, a lower phenol group, or a lower phenol group (a halogen atom or a lower alkyl group) (It may be replaced.) A vinyl group, provided that r ⁴ or r ⁵ is! - ⁶ or the double binding or by Tsu name to Yo Shi One had a _r ⁷ but it may also be shape formed a ring X — represents — 0 —, — S — or Ν — (wherein the formula _Γ represents a hydrogen atom or a lower alkyl group). And a general formula BCOZ [where β is a {nitrogen atom, a nitro group, a cyano group, or a (nitrogen atom or It may be replaced by a vinyl group.) Lower alkyl group, lower alkyl carbonyl group, lower alkoxy carbonyl group , Or equation 1 Ε — r ⁸ (where 1 Ε- Is — O —, — S (O) m-(m 0 2) or one N— (R ^9: hydrogen atom, a lower A Le key Le group) a, r ³ is (c Russia is also rather gain down atom but it may also be substituted by Ma E d le group) lower Ύ zone Les key A halogen group (a halogen atom may be replaced by a halogen atom; a lower phenol group may be substituted); a vinyl group; formula -Ν rather ^{"(r I V, r 1} 1: hydrogen atom also rather lower § Le key Le group ') rather also groups that Re I Table of the oxygen atom, a sulfur atom or窒零atoms And a ^5- to 10-membered heterocyclic group, which may be substituted with a group represented by: (A 5- to 10-membered aromatic heterocyclic group including a phenyl group, a naphthyl group or an oxygen atom, a sulfur atom or a nitrogen atom), and Z is a π-gen atom or a hydride. Oxy group, lower alkoxy group or -0-(acid anhydride). A general formula characterized by reacting with the compound represented by the formula:

 OH ^{(Wherein, r <, r 5, r} 6, r 7, X and Β in. Which are of the meaning same) manufacturing leading frame method of the compounds I Table in. 4. General formula O

[In the formula, R, is a hydrogen atom, Formula-D-r ¹ (In the formula,-D-is-C 0-or-S 0 _2- , and r 'is a lower alkyl group. Or (It may be replaced by a lower phenol or a 2-nitro group.) Indicate a phenyl group. Even if it is substituted with a lower alkoxy group. , A lower alkyl group or a formula (where Y is an oxygen atom)

The child or sulfur atom, shows the r ^z及beauty r ³ are, respectively Re its low-grade A Le key Le group. A) is a group represented by the formula C + The group represented by rr is represented by the formula (wherein, r ⁴ , r ⁵ , r ⁶ , and! ” ⁷ are each a hydrogen atom, a lower alkyl group, or a (halogen group) The atom CI may be substituted by a lower alkyl group or a lower alkyl group.) A phenyl group and η represents 0 or 1. However, η represents When the force is 1, r ⁴ or Γ ⁵ may be combined with Γ ⁶ or r ⁷ to form a double bond or a ring.) Β is {lower nitrogen atom, nitro group, cyano group, (which may be replaced by a nitrogen atom or phenyl group). A Le key group, low grade A Le key Le force Le ball two group, low grade A Le co key imposes Le ball two group, or the formula one E - r ⁸ (wherein one E - is - Ο -, - S (O ) m - (m: 0, 1, 2) Also, (r ^9: a hydrogen atom, a lower A Le key Le group) a, r ⁸ is also (Bruno \ B gain down atoms Or a lower alkyl group, which may be substituted with a phenyl group, or a lower alkyl group, which may be substituted with a gen or molybdenum atom. also lower § Norre key Norre but it may also be substituted with a group) La-et-two group, the formula one N rather _{^{1 * u (r 1 0;}} "r» 1: rather than also hydrogen atom is lower a Le Or a 5- to 10-membered hetero group containing an oxygen atom, a sulfur atom or a nitrogen atom.)) -X- is a suitable factory (a 5- to 10-membered aromatic or heterocyclic group containing a phenyl group, a naphthyl group or an oxygen atom, a sulfur atom or a nitrogen atom). Is  1 2 One 0 —, — S-or one N-(wherein, r ¹² represents a hydrogen atom or a lower alkyl group). ] A herbicide characterized by containing, as an active ingredient, one or more kinds of the compound represented by the formula (I) or a salt thereof.