JP2946656B2 - Uracil derivative and herbicide - Google Patents

Description

[Industrial applications]

The present invention relates to a novel uracil derivative and a selective herbicide containing the derivative as an active ingredient. [Prior art and problems] Conventionally, many herbicides have been put to practical use to protect important crops such as rice, soybean, wheat, corn, cotton, beet, etc. from weeds and increase the productivity of these important crops. Have been. These agents can be broadly classified into three, depending on the application scene, for field action, for paddy fields, and for non-cultivated land. Furthermore, each of them can be classified into a soil mixing treatment type, a pre-emergence soil treatment type, a post-emergence treatment (foliage treatment) type, and the like, depending on the method of applying the medicine. In recent years, with the global population growth, it is clear that the productivity of important crops will affect the food economy of each country. With these changes, it is inevitable that traditional agricultural patterns will change toward the 21st century. In fact, for farmers,
There is an increasing need for the development of herbicides that can economically and efficiently kill or control weeds that hinder crop cultivation as compared to before. As such herbicides, development of drugs having the following conditions has been desired. Low herbicide, high herbicidal effect (especially from the viewpoint of environmental protection, it is necessary to kill weeds by spraying the lowest possible amount of the weeds); It is a problem that long-lasting drugs can damage subsequent crops, and it is important that they show adequate residual efficacy after application.), And those that kill weeds immediately after application (drug treatment) rear,
It is possible to sow and transplant the next crop in a short period of time. The number of times of chemical treatment is small (It is important for farmers to reduce the number of complicated weed control operations as much as possible.) The wide range of weed control targets (broad-leaved weeds, gramineous weeds,
For a weed species having different properties such as a perennial weed, an agent capable of controlling these with one agent is desirable. ), Many methods of re-use (more powerful herbicidal effect can be obtained by combining soil treatment, foliage treatment, etc.) Those that do not show phytotoxicity that poses a problem to crops (mixture of crops and weeds) It is preferable to selectively kill only weeds in such arable land.) However, existing herbicides do not meet all of these requirements. On the other hand, it is known that a specific compound of a uracil derivative exhibits herbicidal activity, for example, The Pesticide Manua
l Eighth Edition, p. 89 The BritishCrop Protection Council (1
987) and the like, Bromacil is described as one of the herbicides having a uracil skeleton. [Means for solving the problem] In view of such a situation, the present inventors show selectivity for important crops, and have an excellent herbicidal effect at a low dose on many weeds, As a result of continuing research to develop a herbicide having both soil treatment and foliage treatment effects, the formula (I)

Where R¹Is a hydrogen atom, C₁~ C₃Alkyl group, hide
Roxymethyl group or C₁~ C₃Table showing haloalkyl groups
Then R^TwoIs C₁~ C₆Represents a haloalkyl group, R^ThreeIs a hydrogen atom, C₁~ C₆Alkyl group, C₁~ C₆Haloalkyl
Group, hydroxymethyl group, halogen atom or nitro group
And R^FourRepresents a hydrogen atom or a halogen atom, and R^FiveRepresents a halogen atom, a nitro group or a cyano group, and R⁶Is -S-B¹[However, B¹Is a hydrogen atom, C₁~ C_FiveAlkyl
Group, C_Three~ C₆Cycloalkyl group, C_Two~ C_FourAlkenyl group, C_Three
~ C_FourAlkynyl group, cyanomethyl group, hydroxymethyl
Group, chloromethyl group, benzyl group, [However, B^{twenty one}Is a hydrogen atom, C₁~ C_ThreeAlkyl group, methylthio
O, represents a phenylthio group or a methoxymethyl group,
B^{twenty two}Represents a hydrogen atom, sodium atom, potassium atom,
Monium group, isopropyl ammonium group, C₁~ C_FiveAl
Kill group, C_Two~ C_FiveAlkenyl group, C_Three~ C_FiveAlkynyl group, C_Three
~ C₆Cycloalkyl group, (C_Three~ C₆Cycloalkyl) C₁~
C_TwoAlkyl group, C_Two~ C_ThreeHaloalkyl group, phenethyl group,
α-methylbenzyl group, 3-dimethylaminopropyl
Group substituted by one or more substituents
Phenyl group (substituent is a halogen atom, C₁~
C_FourAlkyl group, C₁~ C_ThreeAlkoxy group, C₁~ C_TwoAlkyria
Amino group, dimethylamino group, (C₁~ C_TwoAlkoxy) cal
Bonyl group, C_Two~ C_ThreeAcyl group, C₁~ C_TwoHaloalkyl group, C₁
~ C_TwoRepresents a haloalkyloxy group. ) Or 1 or
Benzyl optionally substituted by two or more substituents
Group (however, the substituent is a halogen atom, C₁~ C_FourAlkyl group,
C₁~ C_ThreeAlkoxy group, C₁~ C_TwoAlkylamino group, dimethyl
Ruamino group, C_Two~ C_ThreeAcyl group, trifluoroacetyla
Mino group, (C₁~ C_TwoAlkoxy) carbonyl group, methyls
Ruphonyl group, trifluoromethylsulfonyl group, C₁~ C_Two
Haloalkyl group, C₁~ C_TwoTable showing haloalkyloxy groups
You. ). ], CH_TwoCH_{Two n}CO_TwoB^{twenty two}[However, B^{twenty two}Represents the same meaning as above.
And n represents an integer of 1 to 4. ], CH_Two-Y-B^{twenty three}[However
Then B^{twenty three}Is a hydrogen atom, C₁~ C_FiveAlkyl group, cyanomethyl
Group, C_Two~ C_FiveAcyl group, chloroacetyl group or dimethyl
Represents a carbamoyl group, and Y is an oxygen atom or a sulfur atom
Represents ], CH_Two-Y-CH (B^{twenty one}) CO_TwoB^{twenty two}[However, B^{twenty one}, B
^{twenty two}And Y represent the same meaning as described above. ] Or CH_Two−
Y-CH_TwoCH_{Two n}CO_TwoB^{twenty two}[However, B^{twenty two}, N and Y are as defined above.
Represents the same meaning as ]. ],[However, D^{twenty one}Is a hydrogen atom, C₁~ C_ThreeAlkyl group, C₁~ C_ThreeA
Alkoxy group or (C₁~ C_ThreeAlkoxy) C₁~ C_TwoAlkyl
Represents a group, D^{twenty two}Is a hydrogen atom, C₁~ C_FourAlkyl group, C_Three~ C₆
Cycloalkyl group, C_Two~ C_ThreeHaloalkyl group, phenyl group
Or represents a benzyl group. ],[However, D^{twenty one}And D^{twenty two}Represents the same meaning as described above, and D^{twenty three}
Is a hydrogen atom or C₁~ C_ThreeRepresents an alkyl group. ],[However, D^{twenty two}Represents the same meaning as described above, and D^{twenty four}Is hydrogen field
Child, C₁~ C_ThreeAlkyl group or (C₁~ C_ThreeAlkoxy) C₁~
C_TwoZ represents an oxygen atom, a sulfur atom or NH
Represents ],[However, D^{twenty five}Is hydrogen atom, sodium atom, C₁~ C_FourAl
Kill group, C_Two~ C_FiveAlkenyl group, C_Three~ C_FiveAlkynyl group, C_Two
~ C_FiveAcyl group, C₁~ C_FourAlkylsulfonyl group or (C₁
~ C_ThreeAlkoxy) C₁~ C_TwoRepresents an alkyl group, D²⁶Is C₁~ C
_FourAlkyl group or C₁~ C_ThreeRepresents a haloalkyl group. ],[However, D²⁷Is a hydrogen atom, C₁~ C₆Alkyl group, C_Three~ C₆Shi
Chloroalkyl group, C₁~ C_ThreeHaloalkyl group, C₁~ C_FourArco
Xyl group, C₁~ C_FourAlkylthio group, (C₁~ C_FourAlkoxy)
Carbonyl, mercapto, hydroxyl, (C₁~ C_ThreeArco
Kishi) C₁~ C_TwoAlkyl group, C₁~ C_FourAlkylamino group, ND
²⁸(D²⁹) (However, D²⁸And D²⁹Are each independently C₁~ C_Four
Represents an alkyl group. ), Dimethylcarbamoyl group, CONH
SO_TwoCH_Three, C₁~ C_FourAlkylsulfonyl group or N (D³⁰) S
O_TwoD³¹(However, D³⁰Is hydrogen atom, sodium atom, C₁~ C_Four
Alkyl group, C₁~ C_FourAlkylsulfonyl group, (C₁~ C_ThreeA
Lucoxy) C₁~ C_TwoRepresents an alkyl group, D³¹Is C₁~ C_FourAl
Kill group or C₁~ C_ThreeRepresents a haloalkyl group. ). ],[However, D³²Is C₁~ C₆Alkyl group or C_Three~ C₆Cycloa
Represents a alkyl group. ],[However, D³³, D³⁴And D³⁵Are independently hydrogen sources
Child or C₁~ C₆Represents an alkyl group. ],[However, D³⁶And D³⁷Are each independently a hydrogen atom, C₁
~ C₆Represents an alkyl group or a dimethylamino group. ],[However, D³⁸Is hydrogen atom, halogen atom, mercapto
Group, hydroxyl group, C₁~ C₆Alkyl group, C_Three~ C₆Cycloalkyl
Group, C₁~ C_ThreeHaloalkyl group, C₁~ C_FourAlkoxy group, C₁~
C_FourAlkylthio group, (C₁~ C_FourAlkoxy) carbonyl
Group, dimethylcarbamoyl group, (C₁~ C_ThreeAlkoxy) C₁
~ C_TwoAlkyl group, C₁~ C_FourAlkylamino group, ND
²⁸(D²⁹) (However, D²⁸And D²⁹Has the same meaning as above
Represent. ), CONHSO_TwoCH_Three, C₁~ C_FourAlkylsulfonyl group,
Phenyl, benzyl or N (D³⁹) SO_TwoD³¹(However
Then D³¹Represents the same meaning as described above, and D³⁹Is a hydrogen atom, C₁
~ C_FourAlkyl group, sodium atom, potassium atom, C₁~
C_FourAlkylsulfonyl group or (C₁~ C_ThreeAlkoxy) C₁
~ C_TwoRepresents an alkyl group. ). ],[However, D⁴⁰Is a hydrogen atom, C₁~ C₆Alkyl group, C_Three~ C₆Shi
Chloroalkyl, phenyl, benzyl or 2-py
Represents a lysyl group, D⁴¹Is hydrogen atom, halogen atom, mel
Capto group, hydroxyl group, amino group, C₁~ C₆Alkyl group, C₁~
C_FourAlkylamino group, ND²⁸(D²⁹) (However, D²⁸And D
²⁹Represents the same meaning as described above. ), C₁~ C_FourAlkylthio
Group, CO_TwoD²⁸(However, D²⁸Represents the same meaning as above.
You. ), C₁~ C_FourAlkylsulfonyl group, C₁~ C_FourAlkoki
Group or N (D³⁹) SO_TwoD³¹(However, D³¹And D³⁹Is before
It has the same meaning as described above. ), And D⁴²Is a hydrogen atom,
Logen atom, nitro group, amino group, cyano group, C₁~ C_FourA
Alkylamino group, N (D²⁸) D²⁹(However, D²⁸And D²⁹Is
Represents the same meaning as above. ), C₁~ C_FourAlkyl carboni
Or (C₁~ C_FourAlkoxy) carbonyl group
You. ],[However, D⁴³Is hydrogen atom, hydroxyl group, methoxy group, amino
Group, benzoyl group or C₁~ C_FourRepresents an alkyl group, D⁴⁴
Is hydrogen atom, cyano group, acetyl group, C₁~ C_FourAlkyl
Group, carboxyl group or (C₁~ C_FourAlkoxy) carbo
Represents a nyl group. ],[However, D⁴⁵, D⁴⁶Are each independently a hydrogen atom, phenyl
Group, hydroxyl group, methoxy group or C₁~ C_FourTable showing alkyl groups
You. ] Or[However, D⁴⁷, D⁴⁸Are each independently a hydrogen atom or
C₁~ C_FourRepresents an alkyl group. ]. X is an oxygen atom or
Represents a sulfur atom. Where R^FiveAnd R⁶When forming a ring, formula (II), formula (IV)
-1), formula (IV-2), formula (IV-3) or formula (IV-
4) (Where R¹, R^Two, R^Three, R^FourAnd X have the same meanings as described above.
Stands for A¹Is a hydrogen atom or C₁~ C_FourRepresents an alkyl group, A^TwoIs a hydrogen atom, C₁~ C_FiveAlkyl group, C_Two~ C_FiveAlkenyl
Group, C_Three~ C_FiveAlkynyl group, (C_Three~ C₆Cycloalkyl) C₁
~ C_TwoAlkyl group, C₁~ C₆Haloalkyl group, C₁~ C₆Haloa
Lucenyl group, C₁~ C₆Haloalkynyl group, cyanomethyl
Group, hydroxymethyl group, chloromethyl group, (C₁~ C_ThreeA
Lucoxy) C₁~ C_TwoAlkyl group, -CH_TwoCO_TwoA^{twenty one}[However, A^{twenty one}
Is a hydrogen atom, C₁~ C_FiveAlkyl group, sodium atom, halo
Phenyl or halo optionally substituted with a gen atom
Benzyl group which may be substituted with
You. ], -CH_TwoCON (A^{twenty two}) A^{twenty three}[However, A^{twenty two}And A^{twenty three}Haso
Each independently a hydrogen atom or C₁~ C_ThreeThe alkyl group of
You. ], An optionally substituted phenyl group (provided that
The group is C₁~ C_FourAlkyl group, C₁~ C_FourHaloalkyl group, C₁~ C_Four
Represents an alkoxy group or a halogen atom. ), Replaced
A benzyl group (provided that the substituent is C₁~ C_FourAlkyl
Group, C₁~ C_FourHaloalkyl group, C₁~ C_FourAn alkoxy group, (C₁
~ C_FourAlkoxy) carbonyl group, (C₁~ C_ThreeAlkoxy)
C₁~ C_TwoRepresents an alkyl group or a halogen atom. ) Or -CH
_TwoA^{twenty four}[However, A^{twenty four}Is optionally substituted 2-pyridyl
Group (however, the substituent is C₁~ C_FourAlkyl group or halogen source
Represents a child. ), An optionally substituted 2-pyridazyl group
(However, the substituent is C₁~ C_FourAlkyl group or halogen atom
Represents ), 3-isothiazole group or 3-isooxo
Represents a sasol group. J is a hydrogen atom, C₁~ C_FourAlkyl group, C_Two~ C_FourAlkenyl
Group, C_Three~ C_FourAlkynyl group, hydroxymethyl group, chloro
Methyl group, carbamoylmethyl group, cyanomethyl group,
(C₁~ C_FourAlkoxy) carbonylmethyl group,C_Three~ C₆Cycloalkyl group,(C_Three~ C₆Cycloalkyl) C₁~ C_TwoAlkyl group, (C₁~ C_Two
Alkoxy) C₁~ C_TwoAlkyl group, which may be substituted
Phenyl group (substituent is C₁~ C_FourAlkyl group, C₁~ C_Four
An alkoxy group, (C₁~ C_FourAlkoxy) carbonyl group,
(C₁~ C_FourAlkoxy) C₁~ C_TwoAlkyl group, halogen atom
Represents ) Or an optionally substituted benzyl group (provided that
And the substituent is C₁~ C_FourAlkyl group, C₁~ C_FourAn alkoxy group,
(C₁~ C_FourAlkoxy) carbonyl group, (C₁~ C_FourAlkoki
C) C₁~ C_TwoRepresents an alkyl group or a halogen atom. )
You. ] Is represented. A uracil derivative represented by the following formula (hereinafter referred to as the compound of the present invention)
You. ) Was found. The structural feature of the compound of the present invention is that the 5-position of the uracil ring is
Benze having haloalkyl group and 2-position of uracil ring
R as a substituent on the ring^Four, R^FiveAnd R⁶Unique combination
Is to have. This allows the compound of the present invention to penetrate
It has migratory properties and extremely high herbicidal activity. as a result,
The compounds of the present invention contain more perennial weeds than conventional herbicides.
Soil treatment or foliage treatment for various kinds of weeds
Method and can be applied to extremely low doses.
High effect quickly and without moderate residual effect.
It has a great feature that it can be held together. The compound of the present invention is a field, a paddy field, as a non-cultivated land herbicide,
In both soil treatment and foliage treatment,
Nursing beetle, Korean morning glory, ibis, americanaki
Ngozika, Malva Asagao, Inubeyu, Aobeyu, Ona
Fir, ragweed, sunflowers, cornflowers, yellow
Hair thistle, noborogiku, himejon, dog ash, noha
Ragarashi, Nazuna, Polygonum, Soba Kazura, Swerch
Yu, Shiroza, Koakasa, Butterfly, Hakobe, Oinonu
Fugu, communis, photoenosa, pygmy potato, ko
Nishikinou, Onishikisou, Yaegura, Akane, Su
Broad leaf miscellaneous such as millet, American hornflower, shrimp
Grass, wild sorghum, giant cane, Johnson grass,
Barnyardgrass, crabgrass, oats, ohishiba, enokoro
Grass weeds, such as grasses and sparrows
Cyperaceae Weeds, Spiraea, Omodaka, Urika
Wa, tamayatsuri, suzuki, fireflies and kurowa
Lee, Azena, Konagi, Hirumshiro, Kikasigusa, Taine
It has high herbicidal activity at low dose on various paddy weeds such as biennial.
Important crops such as wheat, corn, barley, soy,
Can be safely used for rice, cotton, beet, sorghum, etc. The compound of the present invention can also be used as a defoliant.
Useful. The compound of the present invention can be prepared, for example, by the methods shown in Schemes 1 to 4.
Therefore, it can be synthesized (R in Schemes 1 to 4)¹, R^Two, R^ThreeR^Four,
R^Five, R⁶And X have the same meanings as described above, and G¹Is a lower class
Represents a alkyl group, G^TwoIs a lower alkyl group or a phenyl group
Represents ). (1) In Scheme 1, β-aminoac
Phenyliso (thio) cyanate to lylic acid ester (V)
(VI) to give a uracil derivative (I '),
After isolation of (I ′) or without isolation, the second step
Derived uracil by alkylating 1st position of uracil ring
2 illustrates a method for producing the body (I). First-stage reaction Usually, (VI) 0.5 to 1.5 equivalents to (V) is preferably used.
Uses 0.9 to 1.1 equivalents. The reaction proceeds without solvent, but usually a solvent is used.
And promoted by. Hexane, hepta as solvent
, Ligroin, aliphatic hydrocarbons such as petroleum ether,
Benzene, toluene, xylene, chlorobenzene, etc.
Halo such as aromatic hydrocarbons, chloroform and methylene chloride
Genated hydrocarbons, diethyl ether, dioxane,
Ethers such as trahydrofuran, acetone, methyl ether
Ketones such as tyl ketone, acetonitrile, isobutyro
Nitriles such as nitriles, pyridine, N, N-diethyla
Tertiary amines such as nilin, formamide, N, N-dimethyl
Acid amides such as tylformamide and N-methylpyrrolidone
-Containing compounds such as dimethylsulfoxide, sulfolane, etc.
Substances, water and mixtures thereof, preferably
Aliphatic hydrocarbons, acid amides, sulfur-containing compounds and
These mixtures can be mentioned. The reaction proceeds without a base.
0.5 to 10 equivalents, preferably 1.0 to 2.0 equivalents. salt
Pyridine, triethylamine, 1,4-diazabi
Nitrogen-containing organic bases such as cyclo [2,2,2] octane, hydrogenation
Sodium, potassium hydride, sodium hydroxide, hydroxyl
Inorganic salts such as potassium chloride, sodium carbonate and potassium carbonate
Group, sodium methoxide, sodium ethoxide,
Metal alcoholates such as lium tert-butoxide
Sodium hydride, sodium hydroxide
And potassium hydroxide. The reaction temperature is usually −40 to 200 ° C., preferably from room temperature.
It is carried out at the reflux temperature of the reaction mixture. The reaction time is generally 10 minutes to 72 hours, preferably 30 minutes.
It takes 24 hours. After the completion of the reaction, a mineral acid such as hydrochloric acid, acetic acid, trifluorovinegar
Acid and organic acid such as p-toluenesulfonic acid.
And (I ′) can be isolated. Second Step: It is preferable to use 1.0 to 10 equivalents of the alkylating agent relative to (I ').
Or 1.0 to 5.0 equivalents. Dime as an alkylating agent
Alkyl sulfates such as tyl sulfate and diethyl sulfate, methyl chloride
, Ethyl chloride, methyl bromide, ethyl bromide, methyl iodide
And halogenated alkyls such as ethyl iodide.
You. The reaction proceeds without solvent, but usually a solvent is used.
And promoted by. Hexane, hepta as solvent
, Ligroin, aliphatic hydrocarbons such as petroleum ether,
Benzene, toluene, xylene, chlorobenzene, etc.
Halo such as aromatic hydrocarbons, chloroform and methylene chloride
Genated hydrocarbons, diethyl ether, dioxane,
Ethers such as trahydrofuran, acetone, methyl ether
Ketones such as tyl ketone, acetonitrile, isobutyro
Nitriles such as nitriles, pyridine, N, N-diethyla
Tertiary amines such as nilin, formamide, N, N-dimethyl
Acid amides such as tylformamide and N-methylpyrrolidone
-Containing compounds such as dimethylsulfoxide, sulfolane, etc.
Substances, water and mixtures thereof, preferably
Aliphatic hydrocarbons, acid amides, sulfur-containing compounds and
These mixtures can be mentioned. Usually 1.0 to 10 equivalents of a base relative to (I ') is preferred.
Uses 1.0 to 2.0 equivalents. Pyridine, trie as base
Tylamine, 1,4-diazabicyclo [2,2,2] octane, etc.
Nitrogen-containing organic bases, sodium hydride, potassium hydride
, Sodium hydroxide, potassium hydroxide, sodium carbonate
And inorganic bases such as potassium carbonate.
Inorganic bases such as sodium hydride and potassium carbonate
It is. The reaction temperature is usually from 0 to 150 ° C, preferably from room temperature.
The reaction is carried out at the reflux temperature of the reaction mixture. The reaction time is generally 10 minutes to 96 hours, preferably 30 minutes.
It takes 48 hours. (2) In Scheme 2, β-aminoac
N-phenylcarbamate (VI
I) to give a uracil derivative (I '),
After isolation of (I ′) or without isolation, the second step
Derived uracil by alkylating 1st position of uracil ring
2 illustrates a method for producing the body (I). First stage reaction Usually, 0.5 to 1.5 equivalents of (VII) relative to (V) is preferred.
Or 0.9-1.1 equivalents are used. The reaction usually requires a solvent.
Aliphatic hydrocarbons such as butane, ligroin and petroleum ether
, Benzene, toluene, xylene, chlorobenzene, etc.
Of aromatic hydrocarbons, chloroform, methylene chloride, etc.
Halogenated hydrocarbons, diethyl ether, dioxa
Ethers such as acetone, tetrahydrofuran, acetone,
Ketones such as tyl ethyl ketone, acetonitrile, iso
Nitriles such as butyronitrile, pyridine, N, N-die
Tertiary amines such as tylaniline, formamide, N, N
-Acids such as dimethylformamide and N-methylpyrrolidone
Sulfur-containing amides, dimethyl sulfoxide, sulfolane, etc.
Yellow compound, methanol, ethanol, propanol,
Alcohols such as ethanol, water and their mixtures
And preferably the above-mentioned aliphatic hydrocarbons and acid amides
, Sulfur-containing compounds and mixtures thereof. Usually 0.5 to 10 equivalents, preferably 1.0 to 2.
Use 0 equivalents. Sodium hydride as base, hydride
Potassium, sodium hydroxide, potassium hydroxide, sodium carbonate
Inorganic bases such as thorium and potassium carbonate, sodium meth
Oxide, sodium ethoxide, potassium tert-butoki
Metal alcoholates such as SID, sodium methylmerca
Metal alkyls such as peptide and sodium ethyl mercaptide
Lumercaptides, preferably hydrogenated sodium
Inorganic bases such as sodium and metal salts such as sodium methoxide
Korats. The reaction temperature is usually from 0 to 200 ° C, preferably from room temperature.
It is performed at the reflux temperature of the mixture. Reaction time is usually from 10 minutes to 72 hours, preferably from 30 minutes.
It takes 12 hours. After the completion of the reaction, a mineral acid such as hydrochloric acid, acetic acid, trifluorovinegar
Acid and organic acid such as p-toluenesulfonic acid.
And (I ′) can be isolated. Step 2 Alkylation under the same reaction conditions as Step 2 in Scheme 1
It can be performed. (3) Scheme 3 shows that one step is N-substituted-β-amino
Acrylic ester (VIII)
The uracil derivative (I) is produced by reacting an anate (VI).
And is performed under the same reaction conditions as in Scheme 1.
be able to. (4) Scheme 4 shows the N-substituted-β-amino in one step
N-phenylcarbamate to acrylate (VIII)
(VII) to produce the uracil derivative (I)
Under the same reaction conditions as in Scheme 2.
Can be. Examples of the synthesis of the compounds of the present invention and intermediates are described below as Examples.
However, the present invention is limited by these.
It is not something to be done. Example A-1 3- (7-Fluoro-3-oxo-4-propargyl)
-2H-1,4-benzoxazin-6-yl) -1-methyl
Ru-6-trifluoromethyl-2,4- (1H, 3H) -pirimi
Synthesis of Zindione (Compound A-1)3- (7-fluoro-3-oxo-4-propargyl-
2H-1,4-benzoxazin-6-yl) -6-trif
0.18 g of fluoromethyl-2,4 (1H, 3H) pyrimidinedione
A suspension containing 0.02 g of sodium hydride (purity 55%)
It was added to a solution of tilformamide (2 ml) at room temperature. 20 minutes
Then, add 0.09 g of dimethyl sulfate and stir overnight.
Was. After distilling off dimethylformamide, add water and add ethyl acetate.
Extracted. Washing with saturated saline, anhydrous sodium sulfate
After drying with ethyl acetate, the ethyl acetate was distilled off to obtain a crude product.
Was. Preparative thin-layer chromatography (developing solvent hexa
(Ethyl acetate = 3: 1) to give 0.15 g of the target compound
Obtained as a color viscous oil. Solidified on standing. Example A-2 3- (7-Fluoro-3-oxo-4-propargyl)
-2H-1,4-benzoxazin-6-yl) -6-tri
Fluoromethyl-2,4 (1H, 3H) -pyrimidinedione
Synthesis of Compound A-2)0.33 g of sodium methoxide and 5 ml of dimethylformamide
3-amino-4,4,4-trifluorocroton
1.10 g of ethyl acid were added at room temperature. 20 minutes later, 6-ethoxy
Carbonylamino-7-fluoro-3-oxo-4-p
Add 1.76 g of ropargyl-2H-1,4-benzoxazine
Heated to 130 ° C. for 4 hours. After cooling to room temperature, pour into ice water
And extracted twice with diethyl ether. Water layer with diluted hydrochloric acid
After acidification, the mixture was extracted three times with ethyl acetate. Ethyl acetate
The extract was washed with saturated saline solution and anhydrous sodium sulfate.
After drying and distilling off ethyl acetate, column chromatography
Purified with chloroform (developing solvent: chloroform)
0.20 g was obtained as pale yellow crystals. Example A-3 3- [7-Fluoro-3-oxo-4- (2-viridi)
Methyl) -2H-1,4-benzoxazin-6-yl]
-1-methyl-6-trifluoromethyl-2,4 (1H, 3H)
-Synthesis of pyrimidinedione (compound A-3)3- (7-fluoro-3-oxo-2H-1,4-benzoo
Xazin-6-yl) -1-methyl-6-triflutro
0.20 g of methyl-2,4 (1H, 3H) -pyrimidinedione was hydrogenated
N, N-dimension in which 0.05 g of sodium chloride (purity 55%) is suspended
It was added to a solution of tilformamide (5 ml) at room temperature. 20 minutes
Thereafter, 0.09 g of 2-chloromethylpyridine hydrochloride was added, and 4
Stirred for hours. After distilling off N, N-dimethylformamide,
And extracted with ethyl acetate. Washing with saturated saline,
After drying over anhydrous sodium sulfate, ethyl acetate is distilled off.
This gave a crude product. Preparative thin-film chromatography (exhibition
Purification with open solvent hexane: ethyl acetate = 2: 3)
0.09 g of the compound was obtained as pale yellow crystals. Example A-4 3- (7-Fluoro-3-oxo-2H-1,4-benzo)
Oxazin-6-yl) -1-methyl-6-trifluoro
Romethyl-2,4 (1H, 3H) -pyrimidinedione (compound A
Synthesis of -4)3- (7-fluoro-3-oxo-2H-1,4-benzoo
Xazin-6-yl) -6-trifluoromethyl-2,4
0.85 g of (1H, 3H) -pyrimidinedione was added to N, N-dimethyl
Dissolve in 8.5 ml of formamide, 0.17 g of anhydrous potassium carbonate,
0.15 ml of methyl iodide was added, and the mixture was stirred for 4 hours. End of reaction
Thereafter, N, N-dimethylformamide is distilled off, water is added,
Extracted with ethyl acetate. Washing with saturated saline, sulfuric anhydride
After drying over sodium, ethyl acetate is distilled off and crude
A product was obtained. This is subjected to column chromatography (development
0.53 g of the target compound in pale yellow
Obtained as crystals. Example B-1 3- (4-chloro-2-fluoro-5-methoxycarbo
Nylmethylthiophenyl) -1-methyl-6-trifluoro
Oromethyl-2,4 (1H, 3H) -pyrimidinedione (compound
Synthesis of B-1)0.16 g of sodium hydride (55% purity) in dimethylform
The suspension was suspended in 5 ml of amide, and 3- (4-chloro-
2-fluoro-5-methoxycarbonylmethylthiophene
Nyl) -6-trifluoromethyl-2,4 (1H, 3H) -pyri
1.5 g of midinedione and 10 ml of dimethylformamide
It was added dropwise at room temperature. After hydrogen generation, dimethyl sulfate
0.59 g was added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture is washed with water 3
It was poured into 00 ml and extracted twice with ethyl acetate. Saturated saline
And dried over anhydrous sodium sulfate, then ethyl acetate
Was distilled off to obtain a crude product. This is a preparative thin layer chromatography
Raffy (Development solvent CHC₃), Then fractionated
High performance liquid chromatography (eluent CHCN: H_TwoO = 5: 1)
Purification gave 0.1 g of the desired compound as a viscous oil. Example B-2 3- (4-Chloro-2-fluoro-5-methoxycarbo
Nylmethylthiophenyl) -6-trifluoromethyl-
2,4 (1H, 3H) -pyrimidinedione (compound B-2)
Success3-Amino-4,4,4-trifur in 50 ml of anhydrous toluene
Add 4.75 g of ethyl olocrotonate solution to sodium hydride
Dimethylformamide suspended in 1.14 g of
To a solution of 110 ml under stirring at 0 ° C. over 15 minutes,
The mixture was further stirred at 0 ° C. for 15 minutes. Then the reaction mixture
Was cooled to -30 ° C, and 4-chloro-2-fluoro-5-
Toxycarbonylmethylthiophenyl isocyanate 6.
A solution of 9 g and 50 ml of anhydrous toluene was added dropwise. Reaction mixture
The mixture was returned to room temperature and stirred for 2 hours. Evaporate the solvent
Then, ethyl acetate was added, and a solution of 2N hydrochloric acid (20 ml) and water (500 ml) was added.
Wash twice, then with saturated saline, anhydrous sodium sulfate
After drying with urea, the ethyl acetate was distilled off to obtain a crude product.
This is subjected to silica gel column chromatography (developing solvent).
CHC₃), Then silica gel column chromatography
Chromatography (developing solvent: ethyl acetate: hexane = 3:
Purify in 1) to obtain 1.5 g of the desired compound as a viscous oil
Was. Example C-1 3- [4-Chloro-2-fluoro-5- (5-methyl
-1,3,4-oxadiazol-2-yl) phenyl]-
1-methyl-6-trifluoromethyl-2,4 (1H, 3H)-
Synthesis of pyrimidinedione (compound C-1)0.31 g of sodium hydride (oil, purity 55%), Dimethi
3-formaldehyde was added to a suspension of 13 ml of formamide at 25 ° C.
-2-fluoro-5- (5-methyl-1,3,4-oxadi
Azol-2-yl) phenyl] -6-trifluorome
Chill-2,4 (1H, 3H) -pyrimidinedione 2.5 g, N, N-di
A solution of 20 ml of methylformamide was added dropwise. hydrogen
After the generation is over, 1.02 g of dimethyl sulfate is added dropwise over 15 minutes.
Was. After stirring at room temperature for 2 hours, water was added and extracted with ethyl acetate.
Was. After drying over anhydrous sodium sulfate, the solvent is distilled off and fractionated.
Liquid chromatography (solvent; acetonitrile: water =
Purification by 5: 1) yielded 0.78 g of the desired product. Example C-2 3- [4-Chloro-2-fluoro-5- (5-methyl
-1,3,4-oxadiazol-2-yl) phenyl]-
6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedi
Synthesis of ON (Compound C-2)1.04 g of sodium hydride (oil, purity 55%), dimethi
To a suspension of ruformamide (75 ml) was added 3-amino-4,0 ° C at 0 ° C.
4.3 g of ethyl 4,4-trifluorocrotonate, 58 m of toluene
l of solution was added dropwise over 15 minutes. 15 minutes at 0 ° C after dropping
After stirring, the mixture was cooled to -30 ° C, and 4-chloro-2-fluoro-
5- (5-methyl-1,3,4-oxadiazole-2-i
Le) Solution of 5.7 g of phenyl isocyanate and 60 ml of toluene
Was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours. The solvent was distilled off under reduced pressure, and 2N hydrochloric acid 13.3 was added to the obtained oil.
ml and 300 ml of water, and extracted twice with ethyl acetate.
Was. The ethyl acetate layer was washed with a saturated saline solution and dried over anhydrous sodium sulfate.
After drying over lithium, the solvent was distilled off.
Preparative liquid chromatography (solvent; acetonitrile: water
= 5: 1) to give 1.78 g of the desired product. Example C-3 3- (4-Chloro-3-ethanesulfonylaminophen)
Nil) -1-methyl-6-trifluoromethyl-2,4 (1
Synthesis of (H, 3H) -pyrimidinedione (compound C-5)3- (3-amino-4-chlorophenyl) -1-methyl
-6-trifluoromethyl-2,4 (1H, 3H) -pyrimidine
Dissolve 0.50 g of dione in 5 ml of pyridine, and
0.16 ml of sulfonyl chloride was added dropwise. 2 o'clock
After the reaction, pyridine was distilled off and dissolved in ethyl acetate.
did. After washing with water, diluted hydrochloric acid and saturated saline, anhydrous sodium sulfate
Drying with lium and evaporation of ethyl acetate gave the crude product.
Was. This is washed with diisopropyl ether and
0.37 g of the compound was obtained as light brown crystals. Example C-4 3- [4-Chloro-3- (N-methyl) ethanesulfo
Nylaminophenyl] -1-methyl-6-trifluoro
Methyl-2,4 (1H, 3H) -pyrimidinedione (compound C-
Synthesis of 6)3- (4-chloro-3-ethanesulfonylaminopheni
L) -1-methyl-6-trifluoromethyl-2,4 (1H,
3H) -pyrimidinedione (0.25 g)
Dissolved in 3 ml of anhydrous potassium carbonate 0.17 g, methyl iodide
0.08 ml was added and the mixture was stirred at room temperature overnight. Dimethylforma
After the amide was distilled off, the residue was dissolved in ethyl acetate,
Washed with water and dried over anhydrous sodium sulfate. Ethyl acetate
The crude product was obtained by distilling off the
Preparative thin-layer chromatography (developing solvent hexane-acetic acid
Purification with ethyl 3: 2) gave 0.18 g of the desired compound.
Was obtained as white crystals. Example C-5 3- [4-Chloro-2-fluoro-5-bis (ethane
Sulfonyl) aminophenyl] -1-methyl-6-tri
Fluoromethyl-2,4 (1H, 3H) -pyrimidinedione
Synthesis of Compound C-10)3- (4-chloro-2-fluoro-5-methanesulfoni
L-aminophenyl) -1-methyl-6-trifluoromethyl
0.50 g of chill-2,4 (1H, 3H) -pyrimidinedione was added at 0 ° C.
And 0.05g of sodium hydride in tetrahydrofuran (5ml)
After adding to the solution, methanesulfonyl chloride
0.11 ml was added dropwise. After 7 hours, add ice water and add ethyl acetate.
Extracted. The ethyl acetate layer was washed with saturated saline and
After drying over sodium sulfate, ethyl acetate is distilled off.
To give a crude product, which was washed with diethyl ether.
Purification yields 0.50 of the target compound as white crystals.
Was. Example C-6 3- (5-acetylamino-4-chloro-2-fluoro)
Rophenyl) -1-methyl-6-trifluoromethyl-
Synthesis of 2,4 (1H, 3H) -pyrimidinedione3- (5-amino-4-chloro-2-fluorophenyl)
L) -1-methyl-6-trifluoromethyl-2,4 (1H,
Dissolve 2.00 g of 3H) -pyrimidinedione in 5 ml of benzene,
0.61 ml of acetic anhydride was added and the mixture was refluxed for 1 hour. Distill benzene
Upon removal, a crude product was obtained, which was washed with hexane,
2.20 g of the desired compound were obtained as white crystals. Melting point 263-266
° C. Example C-7 3- [4-Chloro-2-fluoro-5- (N-acetyl
L) isopropylsulfonylaminophenyl] -1-me
Tyl-6-trifluoromethyl-2,4 (1H, 3H) -pirimi
Synthesis of Zindione (Compound C-14)3- (5-acetylamino-4-chloro-2-fluoro
Phenyl) -1-methyl-6-trifluoromethyl-2,
4 (1H, 3H) -pyrimidinedione (1.00 g) was hydrogenated at 0 ° C.
0.11 g of thorium tetrahydrofuran (10 ml)
After adding to the solution, add isopropylsulfonyl chloride 0.
30 ml was added dropwise. After 2 hours, add ice water and add ethyl acetate
Extracted. The ethyl acetate layer was washed with saturated saline and dried
After drying over sodium sulfate, the ethyl acetate is distilled off.
To give a crude product, which is separated by preparative thin-layer chromatography.
Purify with a solvent (developing solvent hexane-ethyl acetate 2: 1)
This gives 0.54 g of the target compound as a colorless viscous oil.
I got it. Example C-8 3- (4-Chloro-2-fluoro-5-isopropyl)
Sulfonylaminophenyl) -1-methyl-6-trif
Fluoromethyl-2,4 (1H, 3H) -pyrimidinedione (compound
Synthesis of compound C-15)3- [4-chloro-2-fluoro-5- (N-acetyl
L) isopropylsulfonylaminophenyl] -1-me
Tyl-6-trifluoromethyl-2,4 (1H, 3H) -pirimi
Dissolve 0.47 g of Zindione in 5 ml of tetrahydrofuran and add water
Add 0.04 g of sodium oxide and 0.06 ml of water and react for 4 hours.
I let you. Dilute hydrochloric acid was added, and the mixture was extracted with ethyl acetate.
After washing with water and drying over anhydrous sodium sulfate,
Evaporation of the chill gives the crude product, which is
Layer chromatography (developing solvent hexane-ethyl acetate
Purification by 3: 1) yields 0.29 g of the target compound as a colorless viscous
Obtained as a neutral oil. Next, a book synthesized according to the above Examples or schemes
Inventive compounds, including the compounds synthesized in the above Examples,
-A, Table 1-B and Table 1-C,
Physical properties are shown in Tables 2-A, 2-B and 2-C
The compounds of the present invention are limited by these
Not something.  The present invention synthesized according to the above embodiment or scheme
Compounds including the compounds synthesized in the above Examples,
The results are shown in Tables A-1 to 3-C-10.
It is not limited by.  When applying the compound of the present invention as a herbicide,
Generally a suitable carrier such as clay, talc, bentona
Solid carrier such as lite, diatomaceous earth, white carbon or
Water, alcohols (isopropanol, butanol,
Alcohol, furfuryl alcohol, etc.), aromatic
Hydrocarbons (toluene, xylene, etc.), ethers (a
Nisole, etc.), ketones (cyclohexanone, isophoro)
), Esters (butyl acetate, etc.), acid amides (N
-Methylpyrrolidone) or halogenated hydrocarbons
(Such as chlorobenzene)
Surfactants, emulsifiers, dispersions if desired
Agents, penetrants, spreading agents, thickeners, antifreezing agents, anti-caking
Solution, emulsion, wettable powder, dry
Arbitrary dosage forms such as flowables, flowables, powders, granules, etc.
Can be put to practical use. In addition, the compound of the present invention may be used as a preparation or sprayed as required.
Other kinds of herbicides, various insecticides, fungicides, plant growth regulation
It may be applied by mixing with an agent, a synergist and the like. Examples of the types of herbicides to be mixed include, for example,
Chemicals Handbook (Farm Chemi-cals Handboo)
k) Compounds described in the 1989 edition. The application dose of the compound of the present invention depends on the application scene, application time, application
Although there are differences depending on the method, cultivated crop, etc., generally the active ingredient
0.0001 to 10 kg per hectare (ha)
More preferably, about 0.001 to 5 kg is appropriate. Next, the formulation of the formulation when the compound of the present invention is specifically used
Here is an example. However, the formulation examples of the present invention are limited to only these.
It is not something to be done. In the following formulation examples, "parts"
Means part by weight. Formulation Example 1 Water dispersant Compound of the present invention A-1 50 parts Siglite PFP 43 parts (Kaolin-based clay: trade name of Siglite Industrial Co., Ltd.) Solpol 5050 2 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd.) Lunox 1000C 3 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd.) Carplex # 80 (anti-caking agent) 2 parts (White carbon: Shiono The above is uniformly mixed and pulverized into a wettable powder. Formulation Example 2 Milk Compound of the present invention A-1 3 parts Xylene 76 parts Isophorone 15 parts Solpol 3005X 6 parts (mixture of nonionic surfactant and anionic surfactant
Compound: trade name of Toho Chemical Industry Co., Ltd. Formulation Example 3 Flowable agent Compound A-1 of the present invention 35 parts Agrisol S-711 8 parts (Nonionic surfactant: trade name of Kao Corporation) Lunox 1000C 0.5 parts (Anionic surfactant) : Toho Chemical Industry Co., Ltd. 1% Rhodopol water 20 parts (Thickener: Lorne Poulin Co., Ltd.) Ethylene glycol (antifreeze) 8 parts Water 28.5 parts Mix to form a flowable. Formulation Example 4 Granular wettable powder (dry flowable agent) Compound A-1 of the present invention: 75 parts Isoban No. 1: 10 parts (Anionic surfactant: Kuraray isoprene chemical)
(Product name) Vanirex N 5 parts (Anionic surfactant: Sanyo Kokusaku Pulp Co., Ltd.)
Name) Carplex # 80 10 parts (white carbon: trade name of Shionogi & Co., Ltd.) The above components are uniformly mixed and pulverized to form a dry flowable agent.
You. Formulation Example 5 Water dispersant Compound B-1 of the present invention 50 parts Sieglite PFP 43 parts (Kaolin-based clay: trade name of Siglite Industry Co., Ltd.) Solpol 5050 2 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd.) Lunox 1000C 3 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd.) Carplex # 80 (anti-caking agent) 2 parts (White carbon: Shiono The above is uniformly mixed and pulverized into a wettable powder. Formulation Example 6 Emulsion Compound of the present invention B-1 3 parts Xylene 76 parts Isophorone 15 parts Solpol 3005X 6 parts (mixture of nonionic surfactant and anionic surfactant
Compound: trade name of Toho Chemical Industry Co., Ltd. Formulation Example 7 Flowable agent Compound B-1 of the present invention 35 parts Agrisol S-711 8 parts (Nonionic surfactant: trade name of Kao Corporation) Lunox 1000C 0.5 parts (Anionic surfactant) : Toho Chemical Industry Co., Ltd. 1% Rhodopol water 20 parts (Thickener: Lorne Poulin Co., Ltd.) Ethylene glycol (antifreeze) 8 parts Water 28.5 parts Mix to form a flowable. Formulation 8 Granules Compound of the present invention B-1 0.1 part Bentonite 55.0 parts Talk 44.9 parts After uniformly mixing and pulverizing the above, a small amount of water was added and stirred.
Mix and knead, granulate with an extrusion granulator, dry and granulate
You. Formulation Example 9 Granular wettable powder (dry flowable agent) Compound B-1 of the present invention ... 75 parts Isoban No.1 ... 10 parts (anionic surfactant: Kuraray isoprene chemical)
(Product name) Vanirex N 5 parts (Anionic surfactant: Sanyo Kokusaku Pulp Co., Ltd.)
Name) Carplex # 80 10 parts (white carbon: trade name of Shionogi & Co., Ltd.) The above components are uniformly mixed and pulverized to form a dry flowable agent.
You. Formulation Example 10 Water dispersant Compound C-1 of the present invention ... 50 parts Siegrite PFP ... 43 parts (Kaolin based clay: trade name of Siglite Industry Co., Ltd.) Solpol 5050 ... 2 parts (Anionic surfactant: Tono Kagaku Kogyo Co., Ltd.) Lunox 1000C 3 parts (Anionic surfactant: Toho Kagaku Kogyo Co., Ltd.) Carplex # 80 (anti-caking agent) 2 parts (White carbon: Shiono The above is uniformly mixed and pulverized into a wettable powder. Formulation Example 11 Emulsion Compound C-1 of the present invention 3 parts Xylene 76 parts Isophorone 15 parts Solpol 3005X 6 parts (mixture of nonionic surfactant and anionic surfactant
Compound: trade name of Toho Chemical Industry Co., Ltd. Formulation Example 12 Flowable agent Compound C-1 of the present invention 35 parts Agrisol S-711 8 parts (Nonionic surfactant: trade name of Kao Corporation) Lunox 1000C 0.5 parts (Anionic surfactant) : Toho Chemical Industry Co., Ltd. 1% Rhodopol water 20 parts (Thickener: Lorne Poulin Co., Ltd.) Ethylene glycol (antifreeze) 8 parts Water 28.5 parts Mix to form a flowable. Formulation Example 13 Granules Compound C-1 of the present invention 0.1 part Bentonite 55.0 parts Talc 44.9 parts After uniformly mixing and pulverizing the above, a small amount of water was added and stirred.
Mix and knead, granulate with an extrusion granulator, dry and granulate
You. Formulation Example 14 Granular wettable powder (dry flowable agent) Compound C-1 of the present invention: 75 parts Isoban No. 1: 10 parts (Anionic surfactant: Kuraray Isobrene Chemical)
(Product name) Vanirex N 5 parts (Anionic surfactant: Sanyo Kokusaku Pulp Co., Ltd.)
Name) Carplex # 80 10 parts (white carbon: trade name of Shionogi & Co., Ltd.) The above components are uniformly mixed and pulverized to form a dry flowable agent.
You. Use with the above wettable powders, emulsions, flowables, granules
The wettable powder is diluted 50 to 1000 times with water and the active ingredient
Spray so that it will be 0.0001-10kg per hal (ha)
You. Next, the usefulness of the compound of the present invention as a herbicide is described below.
This will be specifically described in a test example. Test Example-1 Herbicidal effect test by soil treatment Sterilized in a plastic box of 15cm long, 22cm wide and 6cm deep
Pile of flooded soil, nobies, crabgrass, kayak rig
Sa, dogwood, cornflower, dogwood, rice,
Mixed corn, wheat, soybean, cotton, about 1 cm
After covering the soil, adjust the soil surface so that the
The surface was evenly sprayed with a small spray. Chemical solution for spraying
Is to dilute the preparation, which is appropriately adjusted according to the above-mentioned formulation examples, with water.
This was used after spraying. 3 weeks after spraying chemicals
The herbicidal effect on weeds and crops is evaluated according to the following criteria.
Did not investigate. The results are shown in Tables 4-A-1 and 4-A-2.
Shown in Tables 4-B, 4-C-1 and 4-C-2
You. Judgment criteria 5: Herbicidal rate 90% or more (almost completely dead) 4: Herbicidal rate 70-90% 3: Herbicidal rate 40-70% 2: Herbicidal rate 20-40% 1: Herbicidal rate 5-20% 0: Herbicidal rate 5% or less (almost no effect) However, the above herbicidal rate is based on the above-ground fresh grass weight in the chemical treatment area.
And the above-ground raw grass weight of the untreated area and the following formula
It is what I sought.Test Example-2 Herbicidal effect test by foliage treatment Sterilized in a plastic box 15cm long, 22cm wide and 6cm deep
Pile of flooded soil, nobies, crabgrass, kayak rig
Sa, dogwood, cornflower, dogwood, rice,
Corn, wheat, soybean, cotton and beet seeds
Each was sown in spots and covered about 1 cm. Various plants
When the product reaches the 2-3 leaf stage, the amount of the active ingredient is a predetermined ratio
And sprayed evenly on the foliage. The chemical solution at the time of spraying is appropriately adjusted according to the above-described formulation examples and the like.
The diluted preparation is diluted with water and used with a small spray.
The seeds were sprayed over the entire foliage. 4 weeks after spraying
The herbicidal effect on various weeds and crops was determined according to Test Example-1.
The survey was conducted according to the standard. The results are shown in Table 5-A-1 and Table 5-A-1.
The results are shown in Tables A-2, 5-B, 5-C-1 and 5-C-2. Test Example-3 Herbicidal effect test under flooded condition Alluvial soil was put in a 1/5000 arel Wagner pot
Then, add water and mix to obtain freshwater conditions with a depth of 2 cm. Thailand
Nubie, konagi, kikasigusa and firefly species
Mix the seeds in the pot above, and add
After placing the tubers of the river, transplant the rice seedlings at the 2.5 leaf stage.
Was. Grow plants by placing pots in a greenhouse at 25-30 ° C,
On the second day after sowing, dilute the drug so that
The diluent was dropped with a female pipette. 3 weeks after dropping medicine
The herbicidal effect on rice and various weeds was tested in Test Example-1.
The investigation was conducted according to the criteria. The results are shown in Table 6. The symbols in each table have the following meanings.N (Novier),M(Mehishiba),K(Cyperus),
H(Inuhozuki),D(Hawkweed),I(Inuga
Rashi),R(Rice),T(corn),W(Com
G),S(Soybean),C(Water),B(Beat) Comparative control compounds are shown below.

Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C07D 405/12 239 C07D 409/10 239 409/10 239 413/10 239 413/10 239 A01N 43/82 101D (72) Inventor Tsutomu Nawamaki 1470 Shirooka, Shirooka-machi, Shiraoka-cho, Minami-Saitama-gun, Saitama Prefecture Nissan Chemical Industry Co., Ltd. 56) References JP-A-1-157977 (JP, A) JP-A-63-41466 (JP, A) JP-A-61-221178 (JP, A) JP-A-4-501567 (JP, A) JP-A Hei 2-501831 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07D 239/54 C07D 413/10 A01N 43/54 A01N 43/82 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] (1) Formula (I) [Wherein, R ¹ represents a hydrogen atom, a C ₁ -C ₃ alkyl group, a hydroxymethyl group or a C ₁ -C ₃ haloalkyl group, R ² represents a C ₁ -C ₆ haloalkyl group, and R ³ represents a hydrogen atom. , C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, a hydroxymethyl group, a halogen atom or a nitro group, R ⁴ represents a hydrogen atom or a halogen atom, R ⁵ is a halogen atom, a nitro group or a cyano represents a group, R ⁶ is -S-B ¹ [However, B ¹ is hydrogen atom, C ₁ -C ₅ alkyl group, C ₃ -C ₆ cycloalkyl group, C ₂ -C ₄ alkenyl group, C ₃
~ C ₄ alkynyl group, cyanomethyl group, hydroxymethyl group, chloromethyl group, benzyl group, CH (B ²¹ ) CO ₂ B ²² [where B ²¹ represents a hydrogen atom, a C ₁ -C ₃ alkyl group, a methylthio group, a phenylthio group or a methoxymethyl group, and B ²² represents a hydrogen atom, a sodium atom, a potassium atom, ammonium group, an isopropyl ammonium group, C ₁ -C ₅ alkyl group, C ₂ -C ₅ alkenyl group, C ₃ -C ₅ alkynyl group, C ₃ -C ₆ cycloalkyl group, (C ₃ -C ₆ cycloalkyl) C ₁ -C ₂ alkyl group, C ₂ -C ₃ haloalkyl group,
Phenethyl group, α-methylbenzyl group, 3-dimethylaminopropyl group, phenyl group optionally substituted by one or more substituents (provided that the substituent is a halogen atom, a C ₁ -C ₄ alkyl group, ₁ -C ₃ alkoxy group, C ₁ ~
Represents a C ₂ alkylamino group, a dimethylamino group, a (C ₁ -C ₂ alkoxy) carbonyl group, a C ₂ -C ₃ acyl group, a C ₁ -C ₂ haloalkyl group or a C ₁ -C ₂ haloalkyloxy group. )
Or a benzyl group optionally substituted by one or more substituents (provided that the substituent is a halogen atom, C ₁
-C ₄ alkyl group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₂ alkylamino group, dimethylamino group, C ₂ -C ₃ acyl group, trifluoroacetyl group, (C ₁ -C ₂ alkoxy) carbonyl It represents group, methylsulfonyl group, trifluoromethylsulfonyl group, a C ₁ -C ₂ haloalkyl group, or a C ₁ -C ₂ haloalkoxy group. ). _{], CH 2 - (CH 2)} n-
CO ₂ B ²² [where B ²² represents the same meaning as described above, and n is 1
Represents an integer of from 4 to 4. ], CH ₂ -Y-B ²³ [However, B ²³ represents a hydrogen atom, C ₁ -C ₅ alkyl group, cyanomethyl group, C ₂ -C ₅ acyl group,
Y represents a chloroacetyl group or a dimethylcarbamoyl group, and Y represents an oxygen atom or a sulfur atom. ], CH ₂ -Y
—CH (B ²¹ ) CO ₂ B ²² [However, B ²¹ , B ²² and Y represent the same meaning as described above. Or CH ₂ —Y—CH ₂ — (CH ₂ ) _n
—CO ₂ B ²² [where B ²² , n and Y represent the same meaning as described above. ]. ], -C (D ²¹ ) = NOCH ₂ CO ₂ D ²² [where D ²¹ is a hydrogen atom, C ₁
Represents a C ₁ to C ₃ alkyl group, a C _{1 to} C ₃ alkoxy group or a (C _{1 to} C ₃ alkoxy) C _{1 to} C ₂ alkyl group, wherein D ²² is a hydrogen atom,
₁ -C ₄ alkyl group, C ₃ -C ₆ cycloalkyl group, C ₂ -C ₃ haloalkyl group, a phenyl group or a benzyl group. -C (D ²¹ ) = NN = C (D ²³ ) CO ₂ D ²² [where D ²¹ and D
²² represents the same meaning as described above, and D ²³ represents a hydrogen atom or C ₁
~C represents a ₃ alkyl group. ^{_{], -CH 2 ZCH (D 24)}} CO 2 D 22 [However, D ²² represents the same meaning as defined above, D ²⁴ represents a hydrogen atom, C ₁ -C ₃ alkyl group or a (C ₁
It represents -C ₃ alkoxy) C ₁ -C ₂ alkyl group, Z is an oxygen atom, a sulfur atom or NH. _{^{], -N (D 25) -SO 2}} D 26 [However, D ²⁵ represents a hydrogen atom, sodium atom, C ₁ -C ₄ alkyl group, C ₂ -C ₅ alkenyl group, C ₃
-C ₅ alkynyl group, C ₂ -C ₅ acyl group, C ₁ -C ₄ alkylsulfonyl group, or a (C ₁ -C ₃ alkoxy) C ₁ -C ₂ alkyl group, D ²⁶ is C ₁ -C ₄ alkyl It represents a group or a C ₁ -C ₃ haloalkyl group. ], [However, D ²⁷ represents a hydrogen atom, C ₁ -C ₆ alkyl group, C ₃ -C ₆ cycloalkyl group, C ₁ -C ₃ haloalkyl group, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio group, (C ₁ -C ₄ alkoxy)
Carbonyl group, mercapto group, hydroxyl group, (C ₁ -C ₃ alkoxy) C ₁ -C ₂ alkyl group, C ₁ -C ₄ alkylamino group, ND
²⁸ (D ²⁹ ) (where D ²⁸ and D ²⁹ are each independently C ₁ -C ₄
Represents an alkyl group. ), Dimethylcarbamoyl group, CONH
SO ₂ CH ₃ , C ₁ -C ₄ alkylsulfonyl group or N (D ³⁰ ) S
O ₂ D ³¹ (where D ³⁰ is a hydrogen atom, a sodium atom, C ₁ -C ₄
Alkyl group, C ₁ -C ₄ alkylsulfonyl group, or a (C ₁ ~
C ₃ alkoxy) represents a C ₁ -C ₂ alkyl group, wherein D ³¹ is C ₁ -C ₄
It represents an alkyl group or a C ₁ -C ₃ haloalkyl group. ). ], [However, D ³² represents C ₁ -C ₆ alkyl or C ₃ -C ₆ cycloalkyl group. ], [However, D ^33, D ³⁴ and D ³⁵ independently represent a hydrogen atom or a C ₁ -C ₆ alkyl group. ], [However, D ³⁶ and D ³⁷ are each independently a hydrogen atom, C ₁
~C represents an _alkyl group or a dimethylamino group. ], [However, D ³⁸ represents a hydrogen atom, a halogen atom, a mercapto group, a hydroxyl group, C ₁ -C ₆ alkyl group, C ₃ -C ₆ cycloalkyl group, C ₁ -C ₃ haloalkyl group, C ₁ -C ₄ alkoxy group, C _1-
C ₄ alkylthio group, (C ₁ -C ₄ alkoxy) carbonyl group, dimethylcarbamoyl group, (C ₁ -C ₃ alkoxy) C ₁
-C ₂ alkyl group, C ₁ -C ₄ alkylamino group, ND
²⁸ (D ²⁹ ) (however, D ²⁸ and D ²⁹ have the same meanings as described above), CONHSO ₂ CH ₃ , C ₁ -C ₄ alkylsulfonyl group, phenyl group, benzyl group or N (D ³⁹ ) SO ₂ D ³¹ (However, D
³¹ represents the same meaning as described above, D ³⁹ is a hydrogen atom, C ₁ -C ₄
Alkyl group, sodium atom, potassium atom, C ₁ -C ₄ alkylsulfonyl group, or a (C ₁ -C ₃ alkoxy) C ₁ -C ₂
Represents an alkyl group. ). ], [However, D ⁴⁰ represents a hydrogen atom, C ₁ -C ₆ alkyl group, C ₃ -C ₆ cycloalkyl group, a phenyl group, a benzyl group or a 2-pyridyl group, D ⁴¹ is a hydrogen atom, a halogen atom, a mercapto group , a hydroxyl group, an amino group, C ₁ -C ₆ alkyl group, C ₁ ~
C ₄ alkylamino group, ND ²⁸ (D ²⁹ ) (however, D ²⁸ and D
²⁹ has the same meaning as described above. ), C ₁ -C ₄ alkylthio group, CO ₂ D ²⁸ (where D ²⁸ has the same meaning as described above), C ₁ -C ₄ alkylsulfonyl group, C ₁ -C ₄ alkoxy group or N (D ³⁹ ) SO ₂ D ³¹ (wherein D ³¹ and D ³⁹ have the same meanings as described above), and D ⁴² is a hydrogen atom, a halogen atom, a nitro group, an amino group, a cyano group, C ₁ -C ₄ An alkylamino group, N (D ²⁸ ) D ²⁹ (where D ²⁸ and D ²⁹ represent the same meaning as described above), a C ₁ -C ₄ alkylcarbonyl group or a (C ₁ -C ₄ alkoxy) carbonyl group. Represents.), [However, D ⁴³ represents a hydrogen atom, a hydroxyl group, a methoxy group, an amino group, a benzoyl group or a C ₁ -C ₄ alkyl group, D ⁴⁴
Represents a hydrogen atom, a cyano group, an acetyl group, C ₁ -C ₄ alkyl group, a carboxyl group or a (C ₁ -C ₄ alkoxy) carbonyl group. ], [However, each represent D ⁴⁵ and D ⁴⁶ are independently a hydrogen atom, a phenyl group, a hydroxyl group, a methoxy group or a C ₁ -C ₄ alkyl group. ] Or [However, D ⁴⁷ and D ⁴⁸ are each independently represent a hydrogen atom or a C ₁ -C ₄ alkyl group. X represents an oxygen atom or a sulfur atom. A uracil derivative represented by the formula: 2. Formula (III) Wherein R ¹ represents a hydrogen atom, a C ₁ -C ₃ alkyl group, a hydroxymethyl group or a halomethyl group, R ² represents a C ₁ -C ₆ haloalkyl group, R ³ represents a hydrogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, a hydroxymethyl group, a halogen atom or a nitro group, R ⁴ represents a hydrogen atom or a halogen atom, R ⁵ represents a halogen atom, a nitro group or a cyano group, B ¹ is a hydrogen atom, C ₁ -C ₅ alkyl group, C ₃ -C ₆ cycloalkyl group, C ₂ -C ₄ alkenyl group, C ₃ -C ₄ alkynyl group, cyanomethyl group, hydroxymethyl group, chloromethyl group, benzyl Group, CH (B ²¹ ) CO ₂ B ²² [where B ²¹ represents a hydrogen atom, a C ₁ -C ₃ alkyl group, a methylthio group, a phenylthio group or a methoxymethyl group, and B ²² represents a hydrogen atom, a sodium atom, a potassium atom, ammonium group, an isopropyl ammonium group, C ₁ -C ₅ alkyl group, C ₂ -C ₅ alkenyl group, C ₃ -C ₅ alkynyl group, C ₃ -C ₆ cycloalkyl group, (C ₃ -C ₆ cycloalkyl) C ₁ -C ₂ alkyl group, C ₂ -C ₃ haloalkyl group,
Phenethyl group, α-methylbenzyl group, 3-dimethylaminopropyl group, phenyl group optionally substituted by one or more substituents (provided that the substituent is a halogen atom, a C ₁ -C ₄ alkyl group, ₁ -C ₃ alkoxy group, C ₁ ~
Represents a C ₂ alkylamino group, a dimethylamino group, a (C ₁ -C ₂ alkoxy) carbonyl group, a C ₂ -C ₃ acyl group, a C ₁ -C ₂ haloalkyl group or a C ₁ -C ₂ haloalkyloxy group. )
Or a benzyl group optionally substituted by one or more substituents (provided that the substituent is a halogen atom, C ₁
-C ₄ alkyl group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₂ alkylamino group, dimethylamino group, C ₂ -C ₃ acyl group, trifluoroacetyl group, (C ₁ -C ₂ alkoxy) carbonyl It represents group, methylsulfonyl group, trifluoromethylsulfonyl group, a C ₁ -C ₂ haloalkyl group, or a C ₁ -C ₂ haloalkoxy group. ). _{], CH 2 - (CH 2)} n -
CO ₂ B ²² [where B ²² represents the same meaning as described above, and n represents 1
Represents an integer of from 4 to 4. ], CH ₂ -Y-B ²³ (where B ²³ represents a hydrogen atom, a C ₁ -C ₅ alkyl group, a cyanomethyl group, a C ₂ -C ₅ acyl group, a chloroacetyl group or a dimethylcarbamoyl group, and Y represents oxygen Represents an atom or a sulfur atom. ], CH
^{_{2 -Y-CH (B 21)}} CO 2 B 22 [However, B ^21, B ²² and Y have the same meanings as defined above. ] Or CH ₂ -Y-CH _2- (C
H _{2) n} -CO ₂ B ²² [However, B ^22, n and Y have the same meanings as defined above. X represents an oxygen atom or a sulfur atom. The uracil derivative according to claim 1, which is represented by the formula: 3. The formula (IV) Wherein R ¹ represents a hydrogen atom, a C ₁ -C ₃ alkyl group or a C ₁ -C ₃ haloalkyl group, R ² represents a C ₁ -C ₆ haloalkyl group, R ³ represents a hydrogen atom, C ₁ -C C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, a hydroxymethyl group, a halogen atom or a nitro group, R ⁴ represents a hydrogen atom or a halogen atom, R ⁵ represents a halogen atom, a nitro group or a cyano group, D ¹ is -C (D ²¹ ) = NOCH ₂ CO ₂ D ²² [where D ²¹ is a hydrogen atom, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ alkoxy group or a (C ₁
-C ₃ alkoxy) C ₁ -C represents a _C2 alkyl group, D ²² is a hydrogen atom, C ₁ -C ₄ alkyl group, C ₃ -C ₆ cycloalkyl group, C ₂
-C ₃ haloalkyl group, a phenyl group or a benzyl group. ], -C (D ²¹ ) = NN = C (D ²³ ) CO ₂ D ²² [where D
²¹ and D ²² represent the same meanings as defined above, D ²³ represents a hydrogen atom or a C ₁ -C ₃ alkyl group. ], -CH ₂ ZCH (D ²⁴ ) C
O ₂ D ²² [where D ²² represents the same meaning as described above, and D ²⁴ represents a hydrogen atom, a C ₁ -C ₃ alkyl group or (C ₁ -C ₃ alkoxy)
Represents a C ₁ -C ₂ alkyl group, and Z represents an oxygen atom, a sulfur atom or NH. ], -N (D ²⁵ ) -SO ₂ D ²⁶ [where D ²⁵ is a hydrogen atom, a sodium atom, a C ₁ -C ₄ alkyl group, a C ₂ -C ₅ alkenyl group, a C ₃ -C ₅ alkynyl group, ₂ -C ₅ acyl group, C ₁
-C ₄ alkylsulfonyl group, or a (C ₁ -C ₃ alkoxy)
It represents C ₁ -C ₂ alkyl group, D ²⁶ represents C ₁ -C ₄ alkyl or C ₁ -C ₃ haloalkyl group. ], [However, D ²⁷ represents a hydrogen atom, C ₁ -C ₆ alkyl group, C ₃ -C ₆ cycloalkyl group, C ₁ -C ₃ haloalkyl group, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio group, (C ₁ -C ₄ alkoxy)
Carbonyl group, mercapto group, hydroxyl group, (C ₁ -C ₃ alkoxy) C ₁ -C ₂ alkyl group, C ₁ -C ₄ alkylamino group, ND
²⁸ (D ²⁹ ) (where D ²⁸ and D ²⁹ are each independently C ₁ -C ₄
Represents an alkyl group. ), Dimethylcarbamoyl group, CONH
SO ₂ CH ₃ , C ₁ -C ₄ alkylsulfonyl group or N (D ³⁰ ) S
O ₂ D ³¹ (where D ³⁰ is a hydrogen atom, a sodium atom, C ₁ -C ₄
Alkyl group, C ₁ -C ₄ alkylsulfonyl group, or a (C ₁ ~
C ₃ alkoxy) represents a C ₁ -C ₂ alkyl group, wherein D ³¹ is C ₁ -C ₄
It represents an alkyl group or a C ₁ -C ₃ haloalkyl group. ). ], [However, D ³² represents C ₁ -C ₆ alkyl or C ₃ -C ₆ cycloalkyl group. ], [However, D ^33, D ³⁴ and D ³⁵ independently represent a hydrogen atom or a C ₁ -C ₆ alkyl group. ], [However, D ³⁶ and D ³⁷ are each independently a hydrogen atom, C ₁
~C represents an _alkyl group or a dimethylamino group], [However, D ³⁸ represents a hydrogen atom, a halogen atom, a mercapto group, a hydroxyl group, C ₁ -C ₆ alkyl group, C ₃ -C ₆ cycloalkyl group, C ₁ -C ₃ haloalkyl group, C ₁ -C ₄ alkoxy group, C _1-
C ₄ alkylthio group, (C ₁ -C ₄ alkoxy) carbonyl group, dimethylcarbamoyl group, (C ₁ -C ₃ alkoxy) C ₁
-C ₂ alkyl group, C ₁ -C ₄ alkylamino group, ND
²⁸ (D ²⁹ ) (however, D ²⁸ and D ²⁹ represent the same meaning as described above), CONHSO ₂ CH ₃ , C ₁ -C ₄ alkylsulfonyl group,
Phenyl group, benzyl group or N (D ³⁹ ) SO ₂ D ³¹ (where D ³¹ has the same meaning as described above, D ³⁹ is a hydrogen atom, C ₁
-C ₄ alkyl group, sodium atom, potassium atom, C ₁ ~
C ₄ alkylsulfonyl group or (C ₁ -C ₃ alkoxy) C ₁
~C represents ₂ alkyl group. ). ], (However, D ⁴⁰ represents a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ cycloalkyl group, a phenyl group, a benzyl group or a 2-pyridyl group, D ⁴¹ represents a hydrogen atom, a halogen atom mercapto group, a hydroxyl group, an amino group, C ₁ -C ₆ alkyl group, C ₁ -C ₄
Alkylamino group, ND ²⁸ (D ²⁹ ) (provided that D ²⁸ and D ²⁹
Represents the same meaning as described above. ), C ₁ -C ₄ alkylthio group, CO ₂ D ²⁸ (where D ²⁸ has the same meaning as described above), C ₁ -C ₄ alkylsulfonyl group, C ₁ -C ₄ alkoxy group or N (D ³⁹ ) SO ₂ D ³¹ (where D ³¹ and D ³⁹ represent the same meaning as described above), and D ⁴² represents a hydrogen atom
Halogen atom, a nitro group, an amino group, a cyano group, C ₁ -C ₄
Arles amino ^{group, N (D 28) D 29} ( where D ²⁸ and D ²⁹ have the same meanings as defined above.) Represents C ₁ -C ₄ alkylcarbonyl group or a (C ₁ -C ₄ alkoxy) carbonyl group . ], [However, D ⁴³ represents a hydrogen atom, a hydroxyl group, a methoxy group, an amino group, a benzoyl group or a C ₁ -C ₄ alkyl group, D ⁴⁴
Represents a hydrogen atom, a cyano group, an acetyl group, C ₁ -C ₄ alkyl group, a carboxyl group or a (C ₁ -C ₄ alkoxy) carbonyl group. ], [However, each represent D ⁴⁵ and D ⁴⁶ are independently a hydrogen atom, a phenyl group, a hydroxyl group, a methoxy group or a C ₁ -C ₄ alkyl group. ] Or [However, D ⁴⁷ and D ⁴⁸ are each independently represent a hydrogen atom or a C ₁ -C ₄ alkyl group. X represents an oxygen atom or a sulfur atom. The uracil derivative according to claim 1, which is represented by the formula: Wherein D ¹ is _{^{-N (D 25) -SO 2 D}} 26 [However, D ²⁵ represents a hydrogen atom, sodium atom, C ₁ -C ₄ alkyl group, C ₂ -C ₅ alkenyl group, C ₃ ~ C ₅ alkynyl group, C ₂ -C ₅ acyl group, C ₁
-C ₄ alkylsulfonyl group, or a (C ₁ -C ₃ alkoxy)
It represents C ₁ -C ₂ alkyl group, D ²⁶ represents C ₁ -C ₄ alkyl or C ₁ -C ₃ haloalkyl group. The uracil derivative according to claim 3, which is represented by the formula: 5. A herbicide comprising the uracil derivative according to claim 1 as an active ingredient.