JPH03120202A - Herbicide for paddy field - Google Patents

Abstract

NEW MATERIAL: The substituted aryl or heteroaryl diones are represented by formula I (Z is a 2-10C alkylene which, as desired, may be substituted with one or more groups selected from a 1-8C alkyl, a 1-8C alkoxy, etc.; O, etc., may be interposed and optional two substituent groups are connected to form a bicyclic or a spiro, etc.; R is phenyl or a 5- or a 6-membered aromatic heterocyclic ring, etc., containing O, etc.; R8 is H, a 1-8C alkyl, a 1-8C alkylcarbonyl, etc.) and related compounds. EXAMPLE: 2,2,6,6-Tetramethyl-4-(3-methoxy-4-methylsulfonyloxy-2-nitrobenzoyl)-2H- pyran-3,5-(4H,6H)-dione. USE: A harbicide for selectively controlling weeds in paddy fields without any phytotoxicity. PREPARATION: A compound represented by formula II is reacted with a base in the presence of a cyanide donor to afford the compound represented by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] This invention relates to novel substituted aryl or heteroarylnoones and related compounds, and their use in controlling paddy field miscellaneous.

[Prior Art] Cyclic 1-one-2-en-3-ol compounds substituted at the 2-position by an aroyl or heteroaroyl group and their enol ethers and enol esters are known herbicidal compounds.

[Purchase of the Invention Co-2-aroyl and 2-heteroaroyl-(cyclic 1-one-2-en-3-ol) compounds (provided that the aroyl or heteroaroyl group has a hydrocarbylsulfonyloxy and/or hydrocarbylsulfonylamino substituent) ) and their enol ethers and enol esters were found to have interesting biological properties. They are suitable for agricultural applications, especially for the control of undesirable vegetation.

More specifically, this invention relates to the general formula [wherein A is a cyclic l-one-2-en-3-ol-2yl residue, and B is -0SOt- or -NSOt-] bonded by a bridge. at least one hydrocarbyl (hydrocarbon residue)
an aryl or heteroaryl group which contains a substituent and may further contain another substituent if desired] and salts thereof, enol ethers and enol esters thereof as active ingredients. It concerns herbicides.

The term hydrocarbyl as used herein means an unsubstituted or substituted hydrocarbon residue. I like hydrocarbon residues! A- contains from 1 to 8 g of carbon atoms, may be straight-chained or branched, saturated or unsaturated, contains or consists of rings which may be saturated, unsaturated or aromatic; be done. Examples of suitable hydrocarbyl substituents are R1! below. It is clear from the definition of

Specifically, the compound constituting the active ingredient of the herbicide for paddy fields according to the present invention has the formula (1) [wherein Z is optionally CI-S alkyl, CI-*alkoxy, CI-*alkylthio, C00R11, halogen cyano] , nitro, phenyl, R@S On', benzyl, N Rlon tr, RttC(0) --S
O*NR1゜Ro and -N(Rho)C(0)R,+
C*-Cr optionally substituted with one or more groups selected from +. alkylene group, and furthermore, in the Z group, an oxygen atom, a group -5 (0
) p-1 group or the group -N(Rho)- may be present, two of the optional alkyl substituents may be linked to form a bicyclic, spiro or bridged alkylene ring, R is phenyl , or a 5- or 6-membered aromatic heterocycle containing one or two heteroatoms selected from oxygen, sulfur and nitrogen, R is 10SO*R+t and -NR1,5O2RI
! and R is optionally substituted with 1 to 6 halogen atoms; CI-S alkyl optionally substituted with 1 to 6 halogen atoms; Optionally substituted CI-. Alkoxy, phenyl, halogen, cyano, nitro, -(0)nS(0)n'Rs', -S Ot
NR+. 'R11', -N (Rr.')C(0)
R11 or -NR+s'5OIRI! ' and two adjacent alkyl substituents may be linked to form a bicyclic alkylene ring, R- is hydrogen, CI- S alkyl, optionally substituted Ct-S alkylcarbonyl, optionally substituted C10, alkoxycarbonyl,
C(0) N R+ s Rt 4, C1-, alkylsulfonyl, P (0) -(OR, +)t, Rt5P
(0) OR0 is an optionally substituted benzoyl or salt-forming moiety, and R and Re'' are independently phenyl, benzyl, or optionally halogen, cyano, CI-t alkoxy or Cl-1 C80, alkyl optionally substituted with one or more groups selected from alkylthio, Rho, Rho, R++, R++, R++ s R
13% R14, 1'l lss R+s' and R1,
are independently hydrogen or C1-, alkyl, Rlt and R1! ' is independently optionally 1 to 6
C2-, which may be substituted with halogen atoms,
alkyl, or optionally C1,-alkyl, ct,
s alkylcarbonyl, CI-@alkoxycarbonyl, CI-S alkylsulfonyl, C(O)N Rt s
R+ 4,P(OXOR,,”), and R,IP(
0) ORII", Rlt is C8,8 alkyl or C1-, alkoxy, Rho is CI-S alkyl, n' and p is independently 0, 1 or 2, and n and S are independently 0 or 1].

The enol compound represented by formula (I) (wherein R1 is H) can exist in several tautomeric forms, with the following being representative.

All of these tautomeric structures are intended to be included within the scope of this invention.

In the preferred compound represented by formula (1), Z is an unsubstituted or substituted c 1-1 alkylene group.

When Z is substituted by Ct-S alkyl, it is preferably substituted by Cl-4 alkyl.

When Z is substituted by Cl-S alkoxy, it is preferably substituted by C1-4 alkoxy.

Z is 01-. When substituted by alkylthio,
It is preferably substituted by Cl-4 alkyldio.

If Z is substituted by halogen, it is preferably bromo, chloro or fluoro.

When the two alkyl substituents of Z are linked to form a bicyclic, spiro or bridged alkylene ring, the alkylene ring preferably has from 1 to 5 carbon atoms.

Preferred substituents for Z are C1-4 alkyl, Sc.

4 alkyl and 5otc+-alkyl.

If an intervening group is present in Z, preferably an oxygen or sulfur atom is present.

When R is a heteroaromatic ring, it is for example thienyl,
Pyrazolyl, pyridyl or pyrimidinyl, preferably a pyrimidinyl ring.

R is preferably substituted phenyl.

If R is further substituted, it is further preferably substituted by 1 or 2 substituents, which substituents are Cl-a alkyl, C-4 alkoxy, N
selected from O, bromo, chloro and fluoro.

When the two alkyl substituents of R are linked to form a bicyclic alkylene ring, the alkylene ring is preferably 3
~4 carbon atoms.

R8, R8, Re', n loq RH6", R,...
R,,',R,,,R,,,RI4,Rl 5% R1
When any of @, R, t, R, , RI7 and Rll is or comprises alkyl, it is preferably C3-4 alkyl.

When any of R8, Rll, R, SR,3, RI7 is or comprises alkoxy, it is preferably C3-4 alkoxy.

R8 is preferably C1,□, alkylcarbonyl,
Cl-8 alkoxycarbonyl, benzoyl, Cl-4
Alkylsulfonyl, or formula % formula % [wherein Rll, R□ and I' (ts are independently a hydrogen atom, optionally 1 to 2 hydroxyl groups, preferably C1-3
C1,-1@ which may be substituted by alkoxy
Alkyl % Cff-4 alkenyl or ILtl and R1 are groups forming c14 alkylene, optionally interrupted by an oxygen atom. An ammonium salt forming moiety represented by t, more preferably t
-butylcarbonyl, isobutylcarbonyl, n-pentylcarbonyl, benzoyl or methylsulfonyl.

When R8 is a salt-forming moiety, -0R6 takes the form -0-+ R6, where Rs is a cationic moiety, which is preferably inorganic, such as l'Ja.

metal equivalents of Ca, Fe or Cu, or organics such as ammonium salt moieties of amines, sulfonium, sulfoxonium or phosphonium moieties. Depending on the nature of R1, the salt may be present in chelate form.

Rll is preferably phenyl or similar C1- optionally substituted with 1 to 3 halogen atoms.
4 alkyl, more preferably phenyl or C4-3 alkyl optionally substituted with 1 to 3 bromine, chlorine or fluorine atoms.

Rll is preferably hydrogen or C1-4 alkyl, more preferably hydrogen.

Compounds belonging to a particular subgroup have the formula (Ia) Rs [wherein R is selected from the group X is oxygen, 5(0)n', CRl' R! ” or N
R38, and R+SR+', R9, Rt', R3 and R4 are independently hydrogen, C3-8 alkyl, Cl-a alkoxy, C
1-, alkylthio or C00Rla, or R1 and R6 together form C5-6 alkylene, or R3 and Rt' together are optionally substituted with 1 to 6 C11 alkyl groups or R8 and R4 together form 03-6 alkylene, R6 optionally substituted with 1 to 6 halogen atoms. Good Cl-1 alkyl, optionally substituted with 1 to 6 halogen atoms, C8-, alkoxy, -(0)nS(0)n'R,, -NR+sSO*
R+t1 is halogen, cyano or nitro, R and R7 are each independently selected from hydrogen or the meaning indicated by R6, provided that at least one of R6, R6 and R7 is a group -osotR1, or - N
Rls S Ot R+ t, R8, Rtt,
Rtt, R88, R18, n and n' have the above-mentioned meanings, and q is 0 or I].

In preferred compounds of formula (Ia), X is oxygen, sulfur or CR, 'R1', more preferably cR
t'Rt'.

R is preferably substituted phenyl.

Substituent Rs -R? and R1, is or comprises a halogen, the halogen is preferably selected from bromo, chloro and fluoro.

R8, Rlo, R,, rtt', R1, R4, R6, R
When any of aqRl, R, Rtt-RtS and RtS is or contains alkyl, it preferably has 1 to 4 carbons.

If R, and R1, R7 and Rt', or R4 and R4 together form alkylene, it preferably has 2 to 5 carbon atoms.

When Rs-Re is or contains Cl-8 alkoxy, it preferably has 1 to 4 carbons.

R3, R0', R7, Rt', R5 and R4 are each preferably hydrogen or C1-4 alkyl. The alkyl more preferably has 1 to 3 carbons.

R6 is preferably -(0)nS (0)n' CI-
4 alkyl, halogen, nitro or Cl-4 alkyl optionally substituted with halogen, more preferably methyl, CF3, C+-3 alkylsulfonyl% C1-3 alkylsulfonyloxy, chloro, bromo or nitro, further Nitro is preferred.

R6 is preferably hydrogen, Cl-t alkyl, C,-4
Alkoxy, Cl-3alkylsulfonyloxy, bromo or chloro. R6 is more preferably hydrogen, methoxy, methylsulfonyloxy or chloro, even more preferably hydrogen.

R7 is preferably bromo, chloro, oso, cl-4
Alkyl, oso, c, -v\roalkyl, OSO, phenyl or NR+5Sotc, -4alkyl.

R7 is more preferably chloro or OSO.

Phenyl or C11, alkylsulfonyloxy, more preferably C1-, alkylsulfonyloxy.

R8 is preferably C1-8 alkylcarbonyl, C
1-, alkoxycarbonyl, benzoyl, C8-4 alkylsulfonyl, or formula% formula% [wherein R□, Rtt and Rf3 are independently hydrogen atoms,
Optionally 1 to 2 hydroxyl groups or C1-.

C1-1g alkyl, C3-4 alkenyl or R11 and R1, which may be substituted by alkoxy,
C may be optionally interrupted by an oxygen atom
, -6 alkylene. ], more preferably t-butylcarbonyl, isobutylcarbonyl, n-pendelcarbonyl, benzoyl or methylsulfonyl.

R11 is preferably phenyl or Cl-4 alkyl optionally substituted with 1 to 3 halogen atoms, further preferably 1 to 3 bromine optionally,
It is phenyl or Cl-3 alkyl which may be substituted with a chlorine or fluorine atom.

R1 is preferably I-1 or C0-4 alkyl, more preferably Ll.

q is preferably 1.

Preferably, R6 is located at the 3rd position, and R6 is shifted to the 4th position.

Preferred compounds have the formula % rusulfonyl or the formula NR, R4,1 [wherein Rt, , Ro and R3 are independently hydrogen atoms,
Cl-18 alkyl, C1-4 alkenyl or Rtl
and Rt2 is −CHt CT(t OCHt CHt
(CHt)-(c Ht)s-like-(C
It is a group forming H, ), -. ] It is. ).

[In the formula, R6 is N 02, Re is H, R7 is osotC
H3 and R8 are C3-8 alkylcarbonyl, C1-
67 In the claims and the description of this specification, R
R111% X5Z-, n s n 1Q Xp and S each have the above meaning unless otherwise specified.

The compound represented by formula (+) that constitutes the active ingredient of the herbicide for rice fields of the present invention is a compound known in the art for the production of 2-aroyl-(cyclic-1,3-dione) and enol ethers or enol esters thereof. This is a new substance that can be produced by a method similar to that of .

More particularly, they can be prepared, for example, by reacting an enol ester of the formula (II) (wherein R and Z have the meanings given above) with a cyanide donor and a moderate base. However, it may be prepared by obtaining a compound (R8 is hydrogen) and then, if desired, producing the corresponding enol ether or enol ester by etherification or esterification.

Similarly, the compound of formula (1a) can be prepared, for example, by reacting an enol ester of the formula (wherein R, X5qSt and R+ R4 are as defined above) with a cyanide donor and a moderate base. IaX (where R6 is hydrogen) can be prepared by obtaining a compound of the formula IaX (where R6 is hydrogen) and then producing the corresponding enol ether or enol ester by etherification or esterification if desired.

The above reaction is carried out in the presence of a catalytic amount of cyan anion donor and/or hydrogen cyanide, with a molar excess of moderate base for the enol ester. The reaction is conveniently carried out using a solvent that is inert under the reaction conditions, such as 1,2-dichloroethane, toluene, acetonitrile,
Methylene chloride, ethyl acetate, dimethylformamide (DMF) or methyl isobutyl ketone (M, IBK)
) is carried out inside. Generally, depending on the reactants and cyanide donor, the rearrangement reaction can be carried out at temperatures below about 80°C. In some cases, for example if problems of excessive by-product formation may arise, the temperature should be kept at a maximum of 40°C.

Preferred cyanide donors are alkali metal cyanides,
For example, sodium and potassium cyanide, cyanohydrins of methylalkylketones having 1-4 carbon atoms in the alkyl group, such as acetone or methylisobutylketone cyanohydrin, cyanohydrins of benzaldehyde or Ct-Cs aliphatic aldehydes, such as acetaldehyde, Cyanohydrins such as propionaldehyde, zinc cyanide, tri(lower alkyl)silyl cyanide, especially trimethylsilyl cyanide and hydrogen cyanide itself. Among the cyanohydrins, a preferred cyanide donor is acetone cyanohydrin. The cyanide donor is used in an amount up to about 50 mole percent based on the enol ester. Generally about 1-10 mole percent cyanide donor is preferred.

The term "moderate base" refers to strong bases such as hydroxides (which may enable hydrolysis of enol esters), and weak bases such as bicarbonates, which act as bases, but whose strength and activity as a base is means a substance located between (that does not function effectively). Moderate bases suitable for use in this reaction include both organic bases such as tertiary amines, and inorganic bases such as alkali metal carbonates and phosphates. Suitable tertiary amines include trialkylamines such as triethylamine, trialkanolamines such as triethanolamine, and pyridine. Suitable inorganic bases include potassium carbonate and trisodium phosphate. This base is the enol ester 1
Amounts of about 1 to about 4 moles per mole are used, preferably about 1.3-2 moles per mole.

When the cyanide donor is an alkali metal cyanide, especially potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are crown ethers.

Depending on the reaction conditions, the keto-enol compound thus obtained can be in the free acid form (R, is H) or in the salt form. When they are in salt form (i.e., R8 is the salt-forming moiety), Ro is an inorganic compound (e.g., NaCa
metal equivalents of SF e or Cu) or organics, such as ammonium salt moieties of amines, sulfonium, sulfoxomium or phosphonium moieties. Depending on the nature of Ro, the salt may exist in chelate form. The salt forms can be converted into the corresponding acid forms (R1 is H) and vice versa in a manner known per se.

Compounds of formula (I) in which R8 is other than hydrogen or a salt-forming moiety can be prepared by methods known per se for the preparation of enol ethers or enol esters from the corresponding enol compounds, such as formula (I) , Rs.
= H) is reacted with a) a group R, -OH and a catalyst, or b) a group Re-Q and a moderate base, where Q is a halogen atom, to form the formula (I) ( However, R8 has the above meaning but is other than hydrogen or a salt-forming moiety).

Reaction a) above is carried out in the presence of a catalyst, for example concentrated sulfuric acid. This reaction is conveniently carried out in a solvent which is also the reactant, such as methanol, at elevated temperature.

Reaction b) above is carried out in the presence of a moderate base, such as triethylamine or pyridine, conveniently at room temperature or below.

Compounds of formula (1) can be recovered from the reaction mixtures in which they are formed by work-up according to established procedures.

The starting materials and reagents used in the methods described herein are known, or if they are not known, they can be prepared by methods analogous to the methods described herein or known methods.

Hereinafter, a method of implementing the present invention will be explained using manufacturing examples. Temperatures are given in degrees Celsius. RT means room temperature.

Parts and percentages are by weight.

[Production Example] Production of the final compound Production Example 1 2.2,6.6-titramethyl-5-(3-methoxy-
Triethylamine (4,9IxQ, 2 equiv. m) and acetone cyanohydrin (1°0 m9) in one portion. After stirring the mixture overnight at RT, it is diluted with water and extracted with ether. Removal of the ether and purification of the residue by PTLC yielded 2,2
,6.6-tetramethyl4-(3-methoxy-4-methylsulfonyloxy-2-nitrobenzoyl)-2H-
Pyran-3,5-(4H,6H)-dione (compound!,
Table A) is obtained.

Production example 2 5-methyl-1-(4-methylsulfonyloxy-2-
chlorobenzoyloxy)-1-cyclohexene-3-
(5,301i+) and 251112 in acetonitrile, triethylamine C3,97z
Q, 2 eq) and acetone cyanohydrin (0, 4x
Q) is added and the mixture is stirred at RT overnight. The acetonitrile is removed, water is added to the residue and extracted with methylene chloride. The organic extracts are combined, washed with dilute HCff and brine, dried and concentrated to dryness. Crystallization of the crude product from ether gives 5-methyl-2-(4-methylsulfonyloxy-2-chlorobenzoyl)cyclohexane-1,3-dione (compound 32, Table A).

Preparation Example 3 Following the procedure of Preparation Examples I and 2, each compound shown in Table A is prepared by rearrangement of the corresponding enol ester.

Production Example 4 2.2,6.6-titramethyl-4-(4-methylsulfonyloxy-2-nitrobenzoyl)-2H-pyran-3,5-(4shi1,6H)-dione (2,54 mmol ) and 2 drops of concentrated sulfuric acid and 20×Q methanol is heated under reflux for 48 hours. Concentrate the reaction mixture and add ether to the residue. The ethereal solution was washed with aqueous sodium bicarbonate and brine, dried,
When concentrated to dryness, 2,2,6,6-titramethyl-4-
(4-Methylsulfonyloxy-2-nitrobenzoyl)-5-methoxy-3,6-cyhydro-2H-pyran-
3-one is obtained.

Production Example 5 2.2,6.6-titramethyl-4-(4-methylsulfonyloxy-2-nitrobenzoyl)-2H-pyran-3,5-(4H,6H)-dione (2.26 mmol) and methylene A solution of acetyl chloride (0.279.3.39 mmol) and 5.0 g of methylene chloride was added to a mixture of chloride (10× and triethylamine (0.471σ, 3.39 mmol)).
Drop at °. The resulting mixture was stirred for 30 minutes, then diluted with methylene chloride, washed, dried, and concentrated to dryness to give 2,2,6,6-titramethyl-4-(4
-methylsulfonyloxy-2-nitrobenzoyl)-
5-acetoxy-3,6-sihydro-2H-pyran-3
-On is obtained.

Preparation Example 6 According to the procedure of Preparation Example 5, correspond to 2,2,6,6-titramethyl-4-(4-methylsulfonyloxy-2nitrobenzoyl)-2H-pyran-3,5-(4H,6H)-dione. By reaction with acyl chloride, the final compound shown in column (■) is prepared.

■ 26.2,2,6,6-titramethyl-4-(4-methylsulfonyloxy-2-nitrobenzoyl)-5-propionyloxy-3,6-sihydro-2H-pyran-
3-on.

27.2.2,6,6-titramethyl-4-(4-methylsulfonyloxy-2-nitrobenzoyl)-5-isobutyryloxy-3,6-sihydro-2H-pyran-
3-on.

28.2.2,6.6-Titramethyl-4-(4-methylsulfonyloxy-2-nitrobenzoyl)=5-pivaloyloxy-3,6-cyhydro2H-pyran-3
-On.

29.2.2,6.6-Titramethyl-4-(4-methylsulfonyloxy-2-nitrobenzoyl)-5-benzoyloxy-3,6-sihydro-2H-pyran-3
-On.

Production Example 7 2-(4-methylsulfonyloxy-2-nitrobenzoyl)cyclohexane-1,3-dione (2°09),
Dichloromethane 5 is added to a solution consisting of triethylamine (0,83!12) and dichloromethane (30!+12).
Benzoyl chloride (0,779) in m12 was added at 0°C and the mixture was stirred at 0°C for 1 hour. The reaction mixture was diluted with dichloromethane, washed with brine, dried over anhydrous sodium sulfate, and purified by silica column chromatography to obtain a solid, which was washed with isopropyl ether and l-
Benzoyloxy-2-(4-methylsulfonyloxy-2-nitrobenzoyl)cyclohexen-3-one (
Compound 60) was obtained.

NMR (ppm from TMS, J:Hz, CDCl
5) 1.8--3.0 (m, 6H), 3, 1 (s
, 31(), 7°2--8.0(m, 8H) Production Example 8 Compound 3 of 3-n-hexanoyloxy-2-(4-methylsulfonyloxy-2-nitrobenzoyl)cyclohexene-3 -one (compound 61, oil) (1,549
) is dione (2,09), n according to Production Example 7 above.
-obtained from hexanoyl chloride (0,769) and triethylamine (0,81(2)).

NMR (same as above) 0.9--1. '5 (m, 9H), 2.
1--3.0 (i, 8H), 7.5 (br, s, 2H
), 7゜8 (br, s, I H) Crocodile■ Sen Senkaku Sen Exploration Fuji Review Work Senuuuuuuuuu Senoo mouth OOOOOOOO (ri OO60000uto) yoi M ff M OPI PI
+v
M M M PI FT
M +w l-1M INP4m OF-
10+/l F-100-+-400+-1+ OOO
-000000000000UCJZCJZOtJZZ
tJUZZtJIJZZZZtJZZZZZZZZZZZZZZZZZZ
Z flash flash
1) Sen I! I= 鴴 1) Flash Flash Flash
Sen Agony = Sen ni 00- Country Sen Sen Sen Sen Sen Sen Sen Sen 1) Q O Tagawa Hatokoshi I! 3 Engineering I! l engineering
Flash Flash Flash Flash Flash Flash Flash Flash
1) Senkokutan: 11 u u u u
u Flash 1) Flash Flash Flash Q Q Flash Flash Flash
Tan Sen =? Takumi P P #1 Sensen taaa t
euuw z tan uu 工 工 1
Sen Ryo Ku Sen Sen Ku Sen Sen x Q O Sen Sen Sen Sen Sen Sen Sen Q ψ's Q Zu Q Add
Q ψ ψ0
i engineering
0
Flash Io 1)1)1) Flash
Flash, flash, flash, flash, flash, flash, flash, flash, flash, flash, flash, flash, flash, flash, flash, flash, flash, flash, flash, flash, flash, flash.
Flash Flash 1) Zu Tech 1) - Flash X υ uuuu
= 1) Sen 1) Ll (J u u Sen Q
Engineering Q Oυ state = 8 吾藁 = 2-containing complex element 3; 1;
Particularly excellent herbicidal activity was shown by compound No. 28.50.53.
54 and 55.

The starting compound, for example, the compound represented by formula (If), is a known compound, or if it is a new compound, it can be produced by a method similar to a known method (Japanese Patent Application No. 1-84630) .

The novel compound represented by the general formula (1) of the present invention can be used as a herbicide for paddy fields. In particular, R6 is 01-
, alkylcarbonyl, CI-, alkoxycarbonyl, benzoyl, Cl-4alkylsulfonyl, or an ammonium salt-forming moiety derived from amine. It shows excellent weeding effect. For example, the common name for the genus Millet. An annual grass in the Poaceae family. A typical harmful grass in rice fields. ), Matsubai (a perennial grass of the family Cyperaceae. Occurs in wetlands, waterways, and rice fields. A typical perennial harmful grass of rice fields), Urikawa (a perennial grass of the family Cyperaceae).

It has a remarkable herbicidal effect on annual and perennial weeds in paddy fields, such as perennial harmful weeds that occur in paddy fields, wetlands, and ditches), firefly, and cyperus (a perennial grass of the Cyperaceae family that occurs in paddy fields, wetlands, and ditches). It exhibits the characteristic of having little drug damage.

Since the compound of the general formula (1) of the present invention exhibits excellent herbicidal activity against weeds before emergence and during the growing season, it can be used, for example, in soil treatment before transplanting paddy rice seedlings, soil treatment after transplantation, and soil treatment during the crop growing season. It is useful as a herbicide for foliage treatment before transplantation and for foliage treatment during crop growth.

By the way, the herbicide of the present invention is generally formulated into a convenient form for use according to conventional methods for agricultural chemical formulations.

That is, the above compound is dissolved in an appropriate inert carrier by blending it in an appropriate ratio together with an auxiliary agent if necessary.
They may be separated, suspended, mixed, impregnated, adsorbed, or adhered to form an appropriate dosage form, such as a suspension, emulsion, solution, wettable powder, powder, granule, or tablet.

The inert carrier that can be used in the present invention may be either solid or liquid, and examples of materials that can be used as solid carriers include soybean flour, grain flour, wood flour, bark flour, saw flour, and tobacco powder. Vegetable powders such as stem flour, walnut flour, mist, type 1 fiber powder, and residue after extracting plant extracts; Textile products such as paper, cardboard, and sifted; Synthetic polymers such as crushed synthetic resins; Clays ( (e.g. kaolin, bentonite, acid clay), talcs (e.g. talc, hyrophyllite),
Silicas (e.g. diatomaceous earth, silica sand, mica, white carbon [synthetic highly dispersed silicic acid, also known as hydrated fine powder silicon or hydrated silicic acid; some products contain calcium silicate as a main component]), activated carbon, sulfur powder, pumice , calcined diatomaceous earth, crushed bricks, fly ash, sand, calcium carbonate, calcium phosphate, and other inorganic mineral powders; chemical fertilizers such as ammonium sulfate, ammonium phosphorus, ammonium nitrate, urea, ammonium chloride, and compost.

These may be used alone or in the form of a mixture of two or more. Materials that can serve as liquid carriers are selected from those that themselves have solvent ability, as well as those that do not have solvent ability but can easily disperse the active ingredient compound with the help of an adjuvant, such as the following: water, alcohols (e.g. methanol, ethanol, isoprobal, butanol, ethylene glycol), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl). ketone, diisobutylketone, cyclohexanone)
, ethers (e.g. ethyl ether, dioxane, cellosolve, dipropyl ether, tetrahydrofuran)
, aliphatic hydrocarbons (e.g. gasoline, mineral oil), aromatic hydrocarbons (e.g. benzene, toluene, xylene, solvent naphtha, alkylnaphthalene), halogenated hydrocarbons (e.g. dichloroethane, chlorinated benzene, chloroform, tetrachloride) carbon), esters (e.g. ethyl acetate, dibdelphthalate, diisopropyl phthalate, dioctyl phthalate), acid amides (e.g. dimethylformamide, diethylformamide, dimethylacetamide), nitriles (e.g. acetonitrile), dimethyl sulfoxide, etc.

The following may be mentioned as adjuvants.

These adjuvants are used depending on the purpose. In some cases, 2 yen! ! Concomitant use of one or more adjuvants. In other cases, no adjuvant may be used at all.

Surfactants are used for the purpose of emulsifying, dispersing, solubilizing or wetting the active ingredient compounds. Examples include: polyoxyethylene alkylaryl ether, polyoxyethylene alkyl ether, polyoxyethylene higher fatty acid ester, polyoxyethylene resin acid ester, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monoole ate, alkylaryl sulfonate, naphthalene sulfonic acid condensate, lignin sulfonate, higher alcohol sulfate ester, etc., for the purpose of dispersion stabilization, adhesion, or binding of the active ingredient compound, for example, the following may be used: May also include casein, gelatin, starch, alginic acid, methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, pine oil, bran oil, bentonite, lignin sulfonate, etc.

For the purpose of improving the flowability of solid products, the following may also be used: waxes, etc., stearates, phosphoric acid alkyl esters, etc.

The following may also be used as peptizers for suspendable products: naphthalene sulfonic acid condensates, condensed phosphates, etc.

It is also possible to add antifoaming agents such as silicone oils.

The combination of active ingredients can be adjusted as necessary. Usually 0.2 to 20% (by weight) when used as a powder or granule, and 0.1 to 50% (by weight) when used as an emulsion or wettable powder.
is appropriate.

Next, examples of typical dosage forms will be given, but it goes without saying that the content of the active ingredient can be varied within the above-mentioned range.

"Parts" in the description indicate parts by weight.

Example 1 Wettable powder compound No. 1 50 parts, Cane clay 20 parts, Clay 2
2 parts of white carbon, 2 parts of sodium lignin sulfonate, and 3 parts of sodium alkylnaphthalene sulfonate are mixed and ground to obtain a wettable powder containing 50% of the active ingredient.

Example 2 Granules Mix 0.35 parts of Compound No. 2, 25 parts of bentonite, 70.65 flll of talc (2 parts of sodium dodecylbenzenesulfonate and 2 parts of sodium ligninsulfonate, and add about 20 parts of water. After kneading with a kneader, it is granulated through a granulator, and then dried and sized to give an active ingredient of 0.35%.
Obtain granules containing.

In order to kill or suppress the growth of various weeds, the herbicide of the present invention is applied to the weeds or to suppress their growth in an amount effective for controlling the weeds or their growth, either as is or in the form of dilution or suspension as appropriate with water, etc. When the emergence or growth of the weed is undesirable, it is used by applying it to the foliage or soil.

The amount of the herbicide of the present invention to be used depends on various factors, such as the purpose, target weeds, weed or crop emergence/growth conditions, weed emergence trends, weather, environmental conditions, dosage form, application method, application location, and application time. fluctuate.

When the herbicide of the present invention is used, for example, as a selective herbicide for paddy rice, the compound of the present invention or its salt may be applied at a rate of 5 to 10,009 per hectare, preferably 10 to 5,002, and more preferably 10 to 5,002 per hectare. is 20~2oog
You can select from the range and process it.

When the herbicide of the present invention is used in combination with other herbicides, the dosage range of the compound of the present invention is even smaller, considering that in many cases it will be effective at a lower dose than when used alone. It is also possible to select from.

The herbicide of the present invention is particularly valuable as a treatment agent for paddy rice weeds from before their emergence to during the growth period, but it can also be used to treat other weeds in order to expand the target weed species and the suitable period for control, or to reduce the amount of the weeds. It is also possible to use them in combination with other agents, which falls within the scope of the present invention.

[Effect of the present invention] The herbicide of the present invention can selectively control paddy field weeds with significantly reduced phytotoxicity to paddy rice. Test examples are shown below, but it goes without saying that the present invention is not limited to these.

Test Example 115000a 7-gunerbot was filled with paddy soil and the flooding depth was set to 4cx. Nobie, Konagi,
Sow the seeds of Japanese cypress and firefly, and embed clumps of omodaka, urikawa, mizugaya tsuri, and black bream, 2
Rice (variety: Koshihikari) in the leaf stage was grown at 6 individuals per pot (
Three 1ax plants and three 3ci plants) were transplanted. After transplant 1
On day 0, granules prepared according to Example 2 were applied to the water surface. A water leakage operation of 3cx1 day was performed on the day after the treatment and the day after.

On the 21st day after treatment, observation and evaluation were performed according to the following criteria. The results are shown in Table 8.

Claims (8)

[Claims] (1) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, Z is C_1_-_8 alkyl, C_1_-
_8 alkoxy, C_1_-_8 alkylthio, COO
R_1_6, halogen, cyano, nitro, phenyl, R
_9SOn, benzyl, -NR_1_0R_1_1, R
_1_2C(O)-, -SO_2NR_1_0R_1_
1 and -N(R_1_0)C(O)R_1_1 is a C_2-C_1_0 alkylene group which may be substituted with one or more groups selected from
In the group, an oxygen atom, a group -S(O)p-
, a group ▲ includes a mathematical formula, a chemical formula, a table, etc. ▼ or a group -N(R_1_6)- may be present,
Two of any alkyl substituents may be linked to form a bicyclic, spiro or bridged alkylene ring, R containing phenyl or one or two heteroatoms selected from oxygen, sulfur and nitrogen. or 6-membered aromatic heterocycle, R is -OSO_2R_1_2 and -NR_1
_5SO_2R_1_2 is substituted with at least one group selected from the group consisting of R_1_2, and R is optionally substituted with 1 to 6 halogen atoms.
_1_-_8 alkyl, optionally substituted with 1 to 6 halogen atoms C_1_-_8 alkoxy, phenyl, halogen, cyano, nitro, -(O)
nS(O)n'R_9', -SO_2NR_1_0'R
_1_1', -N(R_1_0')C(O)R_1_1
or -NR_1_5'SO_2R_1_2', two adjacent alkyl substituents may be linked to form a bicyclic alkylene ring, and R_8 is , hydrogen, C_1_-_8 alkyl, optionally substituted C_1_-_8 alkylcarbonyl, optionally substituted C_1_-_8 alkoxycarbonyl, C(O)NR_1_3R_1_4
, C_1_-_8 alkylsulfonyl, P(O)-(O
R_1_1)_2, R_1_3P(O)OR_1_1,
an optionally substituted benzoyl or salt-forming moiety, R_9 and R_9' are independently phenyl, benzyl, or optionally halogen, cyano, C_1_-_2
C_1_-_8 alkyl optionally substituted with one or more groups selected from alkoxy or C_1_-_2 alkylthio, R_1_0, R_1_0', R_1_1, R_1_1'
, R_1_1", R_1_3, R_1_4, R_1_5
and R_1_6 are independently hydrogen or C_1_-_
8 alkyl, and R_1_2 is C_1_-_8 alkyl optionally substituted with 1 to 6 halogen atoms, or optionally C_1_-_8 alkyl, C_1_-_8
Alkylcarbonyl, C_1_-_8 alkoxycarbonyl, C_1_-_8 alkylsulfonyl, C(O)N
R_1_3R_1_4, P(O)(OR_1_1”)_
2 and R_1_3P(O)OR_1_1'', and R_1_7 is C_1_-_8 alkyl or C_1_-
_8 alkoxy, R_1_8 is C_1_-_8 alkyl, n, n'
and p is 0, 1 or 2, and s is 0 or 1.] A herbicide for paddy fields, characterized in that it contains a compound represented by the following as an active ingredient. (2) Formula ( I a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( I a) [In the formula, R is a group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ X is oxygen, S(O)n', CR_1'R_2' or NR_1_8, R_1, R_1', R_2, R_2', R_3 and R
_4 is independently hydrogen, C_1_-_8 alkyl, C_
1_-_8 alkoxy, C_1_-_8 alkylthio or COOR_1_6, or R_1 and R_2 are taken together to form C_3_-_6 alkylene, or R_2 and R_2' are taken together optionally from 1 to 6 C_1_-_8 Alkylene optionally substituted with a C_1_-_8 alkyl group, or R_3 and R_4 together form C_3_-
_6 alkylene is formed, R_5 is C_1_-_8 alkyl optionally substituted with 1 to 6 halogen atoms, C_1_-_8 alkyl optionally substituted with 1 to 6 halogen atoms;
1_-_8 alkoxy, -(O)nS(O)n'R_1
_2, -NR_1_5SO_2R_1_2, halogen,
is cyano or nitro, and R_6 and R_7 are each independently hydrogen or R_5
However, at least one of R_5, R_6 and R_7 is a group -OSO_2R_1_
2 or -NR_1_5SO_2R_1_2, and R
_8, R_1_2, R_1_5, R_1_6, R_1_
6, n and n' have the meanings according to claim 1, and q is 0 or 1. A herbicide for paddy fields, characterized in that it contains a compound represented by the following as an active ingredient. (3) C_1 in which R_8 may be optionally substituted
_-_8 alkylcarbonyl, optionally substituted C_1_-_8 alkoxycarbonyl, optionally substituted benzoyl, C_1_-_4
Alkylsulfonyl or formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R_2_1, R_2_2 and R_2_3 are independently hydrogen atoms, C_1_ which may be optionally substituted with 1 or 2 hydroxyl groups or C_1_-_3 alkoxy -_1_8 alkyl, C_3_-_4 alkenyl or a group in which R_2_1 and R_2_2 form C_2_-_6 alkylene which may optionally be interrupted by an oxygen atom. The herbicide for paddy fields according to claim 1, which is an ammonium salt-forming moiety derived from an amine represented by the following. (4) R is a group ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The herbicide for paddy fields according to claim 3. (5) The herbicide for rice fields according to claim 4, wherein X is oxygen, CR_1'R_2', R_1' and R_2' are independently hydrogen or C_1_-_4 alkyl, and q is 1. (6) The herbicide for rice fields according to claim 5, wherein R_1, R_2, R_3 and R_4 are independently hydrogen, C_1_-_4 alkyl or C_1_-_4 alkylthio. (7) R_5 is selected from nitro, halogen, C_1_-_4 alkyl and C_1_-_3 alkylsulfonyloxy, C_1_-_3 alkylsulfonyl, and R_
6 is selected from hydrogen, C_1_-_4 alkoxy, halogen and C_1_-_3 alkylsulfonyloxy, and R_7 is halo, C_1_-_3 alkylsulfonyloxy, phenylsulfonyloxy and NHSO_2
The herbicide for rice fields according to claim 6, which is selected from C_1_-_4 alkyl. (8) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_5 is NO_2, R_6 is H, R_7 is OS
O_2CH_3 and R_8 are C_1_-_8 alkylcarbonyl, C_1_-_8 alkoxycarbonyl, benzoyl, C_1_-_4 alkylsulfonyl or formula ▲ Numerical formula, chemical formula, table, etc. ▼ [However, R_2_1, R_2_2 and R_2_3 are independently hydrogen atoms, C_1_ −_1_8 alkyl, C_3_
-_4 alkenyl or R_2_1 and R_2_2 are -CH_2CH_2OCH_2CH_2-, -(CH_
2)_4-, -(CH_2)_5- or -(CH_
2) It is a group forming _6-. ] It is. ) A herbicide for paddy fields, characterized by containing a compound represented by the following as an active ingredient.