GB1574477A

GB1574477A – Benzenesulphonamide derivatives and their use as herbicide
– Google Patents

GB1574477A – Benzenesulphonamide derivatives and their use as herbicide
– Google Patents
Benzenesulphonamide derivatives and their use as herbicide

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Publication number
GB1574477A

GB1574477A
GB40732/77A
GB4073277A
GB1574477A
GB 1574477 A
GB1574477 A
GB 1574477A
GB 40732/77 A
GB40732/77 A
GB 40732/77A
GB 4073277 A
GB4073277 A
GB 4073277A
GB 1574477 A
GB1574477 A
GB 1574477A
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United Kingdom
Prior art keywords
compound
group
formula
allyl
hydrogen atom
Prior art date
1976-10-01
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

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GB40732/77A
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Utsunomiya University

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Utsunomiya University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1976-10-01
Filing date
1977-09-30
Publication date
1980-09-10

1976-10-01
Priority claimed from JP11834376A
external-priority
patent/JPS5344543A/en

1977-05-20
Priority claimed from JP5836977A
external-priority
patent/JPS53145916A/en

1977-08-02
Priority claimed from JP9280377A
external-priority
patent/JPS5427535A/en

1977-09-30
Application filed by Utsunomiya University
filed
Critical
Utsunomiya University

1980-09-10
Publication of GB1574477A
publication
Critical
patent/GB1574477A/en

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legal-status
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Classifications

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS

C07C255/00—Carboxylic acid nitriles

A—HUMAN NECESSITIES

A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING

A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS

A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom

A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond

A01N41/04—Sulfonic acids; Derivatives thereof

A01N41/06—Sulfonic acid amides

Description

PATENT SPECIFICATION ( 11) 1 574 477
l ( 21) Application No 40732/77 ( 22) Filed 30 Sep 1977 ( 19) ( 31) Convention Application No’s 51/118343 ( 32) Filed 1 Oct 1976 52/058369 20 May 1977 ‘t 52/092803 2 Aug 1977 in W) ( 33) Japan (JP) ( 44) Complete Specification Published 10 Sep 1980 ( 51) INT CL 3 C 07 C 143/78 AO 1 N 41/06 ( 52) Index at Acceptance C 2 C200 202 220 226 227 22 Y 30 Y 311 313 314 315 31 Y 323 326 32 Y 338 364 36 Y 385 510 51 X 51 Y 52 Y 534 620 650 652 662 669 697 699 805 Y AA SC SF SG ( 72) Inventors: TETSUO TAKEMATSU MAKOTO KONNAI HIROYOSHI OMOKAWA ( 54) NOVEL BENZENESULFONAMIDE DERIVATIVES AND THEIR USE AS HERBICIDES ( 71) We, UTSUNOMIYA UNIVERSITY, a Japanese National University, of 350 Mine-machi, Utsunomiya-shi, Tochigiken, Japan, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be
performed, to be particularly described in and by the following statement:-
This invention relates to certain novel N,N-disubstituted benzenesulfonamide deriva 5 tives, to a process for their preparation, and to their use as herbicides.
Numerous benzenesulfonamide derivatives have been known For example, Swiss Patent No 224,856 discloses that N-methyl-N-benzoyl-3,4-dichlorobenzenesulfonamide is useful as an insecticide U S Patent 3,245,913 states that N-methyl-N-benzoylsubstituted benzenesulfonamides are effective as bleaching agents Japanese Patent Publication No 10 7216/74 suggests the utilization of N-methyl-N-benzoyl-3, 5-dibromo-6acetoxybenzenesulfonamide as a herbicide.
Elsewhere, Zh Org Chim, 7, 363 ( 1971) reports N-halogenated ethyl-Nsubstituted benzoyl-4-methylbenzene-sulfonamides as known compounds, and Ukrain Khim Zhur, 26, 496 ( 1960) reports N-isopropyl-N-benzoyl-p-chlorobenzene-sulfonamide as a known 15 compound.
It has now been found in accordance with this invention that a certain group of novel N,N-disubstituted benzenesulfonamide derivatives are useful as herbicides, and have superior selective herbicidal activity against the emergency of barnyard grasses (especially, Echinochloa crusgalli Beauv) without substantially affecting rice plants This is surprising 20 in view of the fact that since barnyard grass, the most hazardous weed in a paddy field, is a graminaceous grass, it has been considered as impossible to selectively control barnyard grass without causing phytotoxicity to rice.
The present invention provides a compound of the general formula 25 RO R 1 R R 8 R 30 wherein Ro represents an alkyl group optionally having a substituent selected from a cyano group, lower alkoxy groups and di-(lower alkyl)amino groups, a lower alkenyl group, or a lower alkynyl group; R 1, R 2 and R 3, independently from each other, represent a hydrogen 35 2 1 574 477 2 atom, a halogen atom, a lower alkyl group, or a lower alkoxy group; R 4, R 5, R 6, R 7 and R 8, independently from each other, represent a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group; Y represents a group of the formula O R 9 5 II -C or a group of the formula -CI R 10 o 10 in which one of R 9 and R 10 is a lower alkyl group and the other is a hydrogen atom or a lower alkyl group; with the proviso that when Y is the group 0 1 l 15 -Cand Ro represents an unsubstituted alkyl group, R 4, R 5, R 6, R 7 and R 8 do not represent hydrogen atoms at the same time.
In the present specification and the appended claims, the term “lower” means that a 20 group or radical modified by this term contains up to 6, preferably 1 to 4, carbon atoms.
The term “alkyl group”, as used in the present specification and the appended claims, denotes a saturated aliphatic hydrocarbon group which may be of straight chain or branched chain, and contain generally up to 20, preferably up to 15, more preferably up to 12, carbon atoms Examples of the alkyl group include methyl, ethyl, n or iso-propyl, n-, 25 iso-, sec or tert-butyl, n or neo-pentyl, n-hexyl, n-heptyl, n-octyl, nnonyl, n-decyl, n-undecyl, and n-dodecyl Wherein R O in formula (I) represents an alkyl group, the alkyl group may contain a substituent The substituent is selected from a cyano group (CN), lower alkoxy groups such as a methoxy or ethoxy group, and di(lower alkyl) amino groups such as a dimethylamino or diethylamino group When either one of R 1 to Rs represents a 30 lower alkyl, it is desirably a methyl or ethyl group.
The term “lower alkenyl group” denotes a lower aliphatic hydrocarbon group which contains one carbon-to-carbon double bond, and may be of straight chain or branched chain Examples are vinyl, allyl and butenyl groups, the allyl group being most preferred.
The term “lower alkynyl group” denotes a lower aliphatic hydrocarbon group containing 35 one carbon-to-carbon triple bond A propargyl group is a typical example of the lower alkynyl group.
The term “lower alkoxy group” means a lower alkyl ether group and includes, for example, methoxy, ethoxy, n or iso-propoxy, n-, iso-, sec or tert-butoxy Of these, methoxy and ethoxy groups are preferred 40 The term “halogen atom” denotes fluorine, chlorine, bromine and iodine atoms Of these, a chlorine atom is most preferred, and next comes a fluorine atom.
Thus, preferred substituents R O are alkyl groups containing up to 15 carbon atoms which may contain a substituent selected from a cyano group, lower alkoxy groups and di-(lower alkyl)amino groups; a lower alkenyl group; or a propargyl group Of these; the lower 45 alkenyl groups, above all, an allyl group, and the propargyl group are especially preferred.
Preferred species of R, R 2 and R 3 are a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, and an ethoxy group Preferably, at least one of R,, R 2 and R 3 is a hydrogen atom, and moreover, at least one of these groups is desirably located at the 4-position of the benzene ring to which they are bonded 50 Preferred atoms or groups represented by R 4, R 5, R 6, R 7 and R 8 are a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a methoxy group, and an ethoxy group, the hydrogen atom or halogen atom being especially preferred When at least one of R 4 to R 8 represent the aforesaid groups other than hydrogen, one or two of them are desirably located at the 2-position and/or the 4-position on the benzene ring When Y is a carbonyl 55 group 0 (-C-), 60 1 574 477 it is most preferred that at least one, preferably one or two, of groups R 4 to R 8 be halogen and the remainder be hydrogen If Y is a substituted methylene group -C, R 10 it is most convenient that all of groups R 4 to R 8 be hydrogen atoms at the same time.
Of the compounds of formula (I), a group of preferred compounds are those expressed by the formula Red Ro 2-R 41 R 1 R 11 41 R O el N f ‘v, (X-a) wherein R 01 represents an alkyl group containing up to 15 carbon atoms which may contain a substituent selected from a cyano group, lower alkoxy groups and di(lower alkyl)amino groups, a lower alkenyl group, or a propargyl group; R,1 and R 21, independently from each other, represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, or a methoxy group; R 41, R 51, R 61, R 71 and R 81, independently from each other, represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group; Y 1 represents the group 0 11 -Cor R 91 -CR 10 in which one of R 91 and R 101 is a methyl or ethyl group, and the other is a hydrogen atom or a methyl or ethyl group; with the proviso that when Y 1 is the group CO and R 01 is an unsubstituted alkyl group, R 41, Rs 1, R 61, R 71 and R 81 do not represent hydrogen atoms at the same time.
A group of more preferred compounds of formula (I-a) are those in which R 01 represents an allyl group or a propargyl group and Y 1 represents the group 0 II -CCH 3 -CHCH 3 or -CCH 3 A combination of the group 0 II -Cas Y 1 and an allyl or propargyl group as R 01 ol and a combination of CH 3 -CHor CH 3 -CCH 3 as Y 1 and an allyl group as R 01 are especially advantageous.
Thus, a group of especially preferred compounds of formula (I-a) are those in which Ro 1 represents an allyl or propargyl group; Y 1 represents the group 0 -C-; 4 1 574 477 4 R 41 is a halogen atom; and (a) R 51, R 61, R 71 and R 81 independently from each other, represent hydrogen or a methyl group and R 1, and R 21, independently from each other, represent a hydrogen atom or a methyl group or (b) one of R 51, R 61, R 71 and R 81, especially R 61, is a hydrogen or halogen atom and the rest are hydrogen atoms In case (b), it is preferred that R 1 and R 21, independently from each other, represent a hydrogen atom or a methyl group, especially hydrogen.
Another group of especially preferred compounds of formula (I-a) are those in which R 1 is an allyl gop Yithgroup, Y 1 is the group -CH 3 -CHor CH 3 I -CGil CH 3 R,, represents a hydrogen atom, a halogen atom, or a methyl or methoxy group, R 21 is a hydrogen atom, R 41 and R 61, independently from each other, represent a hydrogen atom, a halogen atom or a methyl group, and R 51, R 71 and R 81 are all hydrogen atoms.
As will be described in detail hereinbelow, the compounds of formula (I) provided by this invention have superior selective herbicidal activity From the view-point of herbicidal activity, most preferred among the compounds of formula (I) are those of the following formula c R (t -be wherein R 02 is an allyl or propargyl group, and X 1 is a hydrogen or chlorine atom; and those of the following formula C Ha-CH-C% 2 1/I-5 O? N -YV 4 J wherein Y 2 is the group CH 3 -CHor CH 3 -CCH 3 and X 2 is a hydrogen or chlorine atom.
Typical examples of the compounds of formula (I) provided by the present invention except those specifically shown in Examples to be given hereinbelow are listed below.
N-allyl-N-( 4-chlorobenzoyl)benzenesulfonamide,.
N-allyl-N-( 3,4-dichlorobenzoyl)benzenesulfonamide, N-allyl-N-( 2,5-dichlorobenzoyl)benzenesulfonamide, N-allyl-N-( 3,5-dichlorobenzoyl)benzenesulfonamide, N-allyl-N-(pentachlorobenzoyl)benzenesulfonamide, and N-allyl-N-benzoylbenzenesulfonamide.
Specific examples of the most preferred compounds in the present invention are:
N-allyl-N-( 2-chlorobenzoyl)benzenesulfonamide, N-allyl-N-( 2,4-dichlorobenzoyl)benzenesulfonamide, N-propargyl-N-( 2-chlorobenzoyl)benzenesulfonamide, N-allyl-N-(a,a-dimethylbenzyl)benzenesulfonamide, N-allyl-N-(a-methylbenzyl)benzenesulfonamide, N-allyl-N-(a-methyl-4-chlorobenzyl)benzenesulfonamide, and N-allyl-N-(a,a-dimethyl-4-chlorobenzyl)benzenesulfonamide.
1 574 477 Cl C) 1 574 477 5 According to the present invention, the compound of formula (I) can be produced by (a) reacting a benzenesulfonamide derivative of the general formula Rlj 4 i RO R 502-N-M 5 wherein M represents a hydrogen atom or an alkali metal atom, and R 0, R 1, R 2 and R 3 are as defined hereinabove, with a compound of the general formula R 4, R 5 10 R 8 R 7 wherein X 3 is a halogen atom, and R 4, R 5, R 6, R 7, R 8 and Y are as defined hereinabove, or 15 (b) reacting a benzenesulfonyl halide of the general formula RI.
a T (iv) R R 3 t (IV) 20 wherein X 4 is a halogen atom, and R 1, R 2 and R 3 are as defined hereinabove, with a compound of the general formula R 4 Rs 25 u N -y / –< R (v) RB Rwherein R 0, R 4, Rs, R 6, R 7, R 8 and Y are as defined hereinabove, or (c) reacting a compound of the general formula 30 M R 4 R 5 52950-N-Y Rh ^T R X == (\J 17) Ra R 8 R 7 35 wherein R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, Y and M are as defined hereinabove, with a compound of the formula Ro X 4 (VII) 40 wherein X 4 is a halogen atom, and R O is as defined above. The reaction of the benzenesulfonamide derivative of formula (II) with the compound of formula (III) in method (a) may be carried out in the absence of a solvent Generally, however, it is preferably carried out in an inert solvent Examples of usable solvents are water, ethers such as diethyl ether, dioxane or tetrahydrofuran, aromatic hydrocarbons 45 such as benzene, toluene or xylene, N,N-dimethyl formamide, dimethyl sulfoxide, and pyridine For certain types of the starting materials, alcohols such as methanol or ethanol, ketones such as acetone or methyl ethyl ketone, or halogenated hydrocarbons such as methylene chloride, chloroform or carbon tetrachloride may also be used as the solvents. These solvents are used singly or as mixtures of two or more 50 The reaction temperature is not critical, and can be varied over a wide range according, for example, to the types of the starting materials, and the type of the solvent. Advantageously, the reaction temperature is generally from about O C to the reflux temperature of the reaction mixture, preferably from room temperature to the reflux > temperature of the reaction mixture It is sufficient that the reaction pressure is atmospheric 55 pressure, but if desired, reduced or elevated pressures may be employed Under these conditions, the reaction can be terminated in about 0 5 to 5 hours.
The ratio between the compound of formula (II) and the compound of formula (III) to be reacted is not critical, and can be varied over a wide range Advantageously, the compound of formula (III) is used in an amount of generally at least 1 mole, preferably 1 1 to 2 moles, 60 per mole of the compound of formula (II).
If a compound of formula (II) in which M is a hydrogen atom is used as the starting material, the above reaction is advantageously carried out in the presence of an acid binder.
Examples of usable acid binders are basic substances, for example alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, and organic bases such as pyridine or 65 r 6 1 574 477 6 triethylamine.
Examples of preferred alkali metal atoms for M in formula (II) are lithium, potassium and sodium A compound of formula (II) in which M is an alkali metal atom may be prepared in advance from a compound of formula (II) in which M is a hydrogen atom and an alkali metal hydride such as sodium hydride or potassium hydride or an alkali metal such 5 as sodium or potassium, and then reacted with the compound of formula (III) Or it may be formed in situ by causing the alkali metal hydride or alkali metal to be present in the reaction system.
Thus, in the reaction between the compound of formula (II) and the compound of formula (III), the use of a reaction medium comprising a combination of sodium hydroxide 10 or potassium hydroxide and water; a combination of pyridine and an ether or an aromatic hydrocarbon; or a combination of an alkali metal hydride and N,N-dimethyl formamide or dimethyl sulfoxide is advantageous.
The amount of each of the alkali metal hydroxide, organic base, alkali metal hydride, etc.
may be at least 1 mole, preferably 1 1 to 3 moles, per mole of the compound of formula (II) 15 In the compound of formula (III), a chlorine atom is especially preferred as the halogen atom represented by X 3.
The method (a) can be especially advantageously applied to the production of compounds of formula (I) in which Y represents 20 O R 9 CH 3 11 1 1 -C or -CH such as -CHThe resulting reaction mixture containing the compound of formula (I) can be recovered 25 by a known procedure For example, water is added to the reaction mixture, and when the final product precipitates as a solid, it can be separated by filtration, centrifugal separation or the like When the final product precipitates as an oil, it can be separated by solvent extraction, decantation or the like In the case of solvent extraction, benzene, ethyl acetate, and chloroform may be suitably used as solvents The crude final product separated can be 30 purified, as needed, by recrystallization, distillation, chromatography, etc.
According to method (b) in accordance with this invention, the benzenesulfonyl halide of formula (IV) is reacted with the amine of formula (V) This reaction can be performed in the absence of a solvent, but usually, it is preferred to carry it out in an inert solvent.
Examples of useful inert solvents are water, aromatic hydrocarbons such as benzene, 35 toluene or xylene, ethers such as diethyl ether, tetrahydrofuran or dioxane, ketones such as acetone or methyl ethyl ketone, and halogenated hydrocarbons such as methylene chloride, chloroform or carbon tetrachloride Water, benzene, and tetrahydrofuran are especially preferred.
The reaction temperature is not critical, and can be varied over a wide range according, 40 for example, to the type of the starting materials and/or the type of the solvent used It is advantageous that the reaction temperature is generally from about O C to the reflux temperature of the reaction mixture, preferably from room temperature to about 80 ‘C The reaction pressure is usually atmospheric pressure, but if desired, elevated or reduced pressures may be employed 45 If desired, the reaction in method (b) may be carried out in the presence of a catalyst.
Useful catalysts are, for example, alkali metal hydroxides such as sodium hydroxide, and organic bases such as pyridine or triethylamine The amount of the compound of formula (IV) is advantageously about 1 to 2 moles per mole of the compound of formula (IV).
The ratio between the compound of formula (IV) and the compound of formula (V) is 50 neither critical and can be varied over a wide range Generally, it is advantageous that the compound of formula (IV) is used in an amount of at least 1 mole, preferably 1 1 to 2 moles, per mole of the compound of formula (V).
Under the reaction conditions described hereinabove, the reaction is generally terminated in about 1 to 6 hours The separation of the final product from the reaction 55 mixture and its purification can be performed in the same manner as mentioned hereinabove with regard to method (a).
In method (c) of this invention, the compound of formula (VI) is treated with an alkylating, alkenylating or alkynylating agent lthe compound of formula (VII)l to introduce the group Ro into the N-atom of the compound of formula (VI) 60 Examples of the compound of formula (VII) include alkyl halides such as methyl bromide, ethyl chloride, methyl iodide, n-butyl iodide and n-decyl bromide, substituted alkyl halides such as cyanomethyl bromide, methoxypropyl iodide and dimethylaminopropyl bromide, alkenyl halides such as allyl chloride, and alkynyl halides such as propargyl chloride 65 1 574 477 1 574 477 Preferably, the reaction between the compound of formula (VI) and the compound of formula (VII) is generally carried out in an inert solvent Useful solvents include, for example, ethers such as diethyl ether, tetra-hydrofuran or dioxane, aromatic hydrocarbons such as benzene, toluene or xylene, alcohols such as methanol or ethanol, ketones such as acetone or methyl ethyl ketone, halogenated hydrocarbons such as methylene chloride or 5 chloroform, N,N-dimethyl formamide, dimethyl sulfoxide, pyridine, and water.
Advantageously, the reaction of a compound of formula (VI) in which M is hydrogen with the compound of formula (VII) can be carried out in the presence of a basic catalyst, for example an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an organic base such as sodium hydride or potassium hydride, or an alkali metal such as 10 metallic sodium or potassium The catalyst can be used in an amount of 1 to 2 moles per mole of the compound of formula (VI) A compound of formula (VI) in which M is an alkali metal atom can be prepared by the reaction of a compound of formula (VI) in which M is hydrogen with the alkali metal hydride or alkali metal It may also be produced in situ in the reaction system 15 The reaction temperature is not critical, and can be varied widely according, for example, to the types of the starting materials, or the type of the solvent Generally, the reaction temperature is from about O C to the reflux temperature of the reaction mixture, preferably from room temperature to the reflux temperature of the reaction mixture.
Usually, the reaction pressure is atmospheric pressure, but if desired, reduced or elevated 20 pressures may be used.
The ratio between the compound of formula (VI) and the compound of formula (VII) is not critical, and can be varied widely The compound of formula (VII) is used in an amount of at least 1 mole, usually 1 2 to 3 moles, per mole of the compound of formula (VI).
Under the reaction conditions described hereinabove, the reaction can be terminated in 25 about 1 to 10 hours The final product of formula (I) can be obtained in good yields from the resulting reaction mixture in the same manner as described hereinabove.
Some of the compound of formula (VI) used in method (c) in this invention, especially those in which Y is the group 30 R 9 I -CR 1 i O 35 are novel compounds, and can be prepared, for example, by reacting correspondingly substituted benzylamines with the corresponding benzenesulfonyl halides in the presence of catalysts such as sodium hydroxide.
The production of the compound (I) of this invention is illustrated by the following 40 Examples.
EXAMPLE 1
N-Methyl-N-(a, a-dimethylbenzyl) benzenesulfonamide 27 5 g ( 0 1 mole) of N-(a,ac-dimethylbenzyl)benzenesulfonamide was added to 5 8 g ( 0 12 45 mole) of 50 % sodium hydride in 200 ml of dry N,N-dimethyl formamide The mixture was stirred at room temperature for 30 minutes to react them To the resulting sodium salt of N-(aa-dimethylbenzyl benzenesulfonamide was added 16 1 g ( 0 17 mole) of methyl bromide The mixture was heated to 60 C and stirred for 1 hour The N,Ndimethyl formamide was distilled off under reduced pressure, and cold water was added The 50 resulting white solid was recrystallized from methanol to afford N-methylN-(a,adimethylbenzyl)benzenesulfonamide in a yield of 87 % This compound is designated as compound No 64 in Table 2 below, and its melting point and elemental analysis values are shown in Table 2.
The N-(a,a-dimethylbenzyl)benzenesulfonamide used as a starting compound in the 55 above procedure could be prepared in the following manner A two-layered mixture consisting of 33 8 g ( 0 25 mole) of a,a-dimethylbenzylamine and 120 nl of a 10 % aqueous solution of sodium hydroxide was stirred at below 40 C, and 44 1 g of benzenesulfonyl chloride was added dropwise Stirring the mixture for an additional 1 5 hours afforded a white precipitate The solid precipitate was collected by filtration, and recrystallized from 60 methanol to afford N-(a,a-dimethylbenzyl)benzenesulfonamide having melting point of 114 to 115 C in a yield of 67 %.
Starting compounds shown in Table 1 were prepared by the same procedure as above except that a-methyl-benzylamine or the correspondingly substituted a,adimethylbenzylamines were used instead of the a,a-dimethylbenzylamine, and the 65 8 1 574 477 8 correspondingly substituted benzenesulfonyl chlorides were used instead of the benzenesulfonyl chloride.
TABLE 1
Q, c, 3 a.
Qjjj 2 35 OC-NM ? Q-5 a Compound No.
Q 1 Q 2 Q 3 Q 4 Melting point or refractive index 2 2-CH 3 3 4-CH 3 4 4-CH 30 5 4-Ce 6 2-CH 3 7 4-C 2 H 5 8 H 9 H 10 H 11 4-CH 3 12 4-C 2 H 5 13 4-Ce 14 2-CH 3 15 2-CH 3 H H H H 5-CH 3 H H H H H H H 4-CH 3 5-CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 H H H H H H H H H H H H CH 3 H H H IT H H 121 C.
137 C.
128 130 C.
126 C.
112 0-112 5 C.
103 5-104 0 C 107 C.
72 78 C.
102 103 C.
82 83 5 C.
n 6 = 1 5656 74 75 C.
104 5-105 C.
72.5-73 C.
Compounds Nos 65 to 88 and 95 to 102 shown in Table 2 could be produced in the same way as in Example 1 using the starting compounds Nos 2 to 15.
EXAMPLE 2
N-Allyl-N-(a-methyl-2-chlorobenzyl)benzenesulfonamide 1.97 g ( 0 01 mole) of N-allylbenzenesulfonamide was added to 0 58 g ( 0 012 mole) of % sodium hydride in 15 ml of dry N,N-dimethylformamide The mixture was stirred at room temperature for 30 minutes to react them To the resulting sodium salt was added 2 10 g ( 0 012 mole) of a-methyl-2-chlorobenzyl chloride The mixture was stirred at room temperature for 1 hour The N,N-dimethyl formamide was distilled off under reduced pressure, and cold water was added The resulting oil layer was extracted with benzene.
The benzene layer was dried over anhydrous magnesium sulfate, concentrated, and purified by silica gel chromatography to afford the final product The final product is designated as compound No 89 in Table 2, and its melting point and elemental analysis values are shown in Table 2.
Compounds Nos 90 to 94 shown in Table 2 could be prepared in the same way as in Example 2.
EXAMPLE 3
N-methyl-N-( 2-chlorobenzoyl)benzenesulfonamide 1.71 g ( 0 01 mole) of N-methylbenzenesulfonamide was added to 0 58 g ( 0 012 mole) of % sodium hydride in 15 ml of dry N,N-dimethylformamide The mixture was stirred at room temperature for 30 minutes to react them To the resulting sodium salt was added 2 10 g ( 0 012 mole) of 2-chlorobenzoyl chloride, and the mixture was stirred at room 1 574 477 1 574 477 temperature for 1 hour The N N-dimethyl formamide was distilled off under reduced pressure Cold water was added, and the resulting oil layer was extracted with benzene The benzene layer was dried over anhydrous magnesium sulfate, and concentrated to afford almost pure N-methyl-N-( 2-chlorobenzoyl)benzenesulfonamide in a yield of 92 % For further purification, this compound was subjected to chromatography or high vacuum 5 distillation This compound is designated as compound No 16 in Table 2, and its melting point and elemental analysis values are shown in Table 2.
Compounds Nos 17 to 63 in Table 2 could be prepared in the same way as in Example 3.
EXAMPLE 4 10
N-Allyl-N-( 2-chlorobenzoyl)benzenesulfonamide 3.0 g ( 0 01 mole) of N-2-chlorobenzoyl benzenesulfonamide prepared from benzenesulfonamide and 2-chlorobenzoyl chloride was added to 0 58 g ( 0 012 mole) of 50 % sodium hydride in 15 ml of dry tetrahydrofuran After stirring for 30 minutes at room temperature, 1 48 g ( 0 012 mole) of allyl bromide was added Then the mixture was reacted for 2 hours 15 under the same conditions The tetrahydrofuran was distilled off under reduced pressure, and cold water was added The resulting oil layer was extracted with benzene The benzene layer was separated, dried over anhydrous magnesium sulfate, and concentrated to afford a white solid Recrystallization from methanol afforded compound No 27 in Table 2 in a yield of 35 % 20 Compounds Nos 16 to 26 and 28 to 63 could be produced in the same way as in Example 4.
EXAMPLE 5
N-Methyl-N-(a-methylbenzyl)benzenesulfonamide 25 Benzenesulfonyl chloride ( 2 1 g; 0 012 mole) was added dropwise at below 40 WC to a two-layered mixture consisting of 1 35 g ( 0 01 mole) of N-methyl-aphenethylamine lprepared by the method disclosed in Novzlli, J Ame Chem Soc 61, 520 ( 1939)l and 12 ml of a 10 % aqueous solution of sodium hydroxide On continuing the reaction for 2 hours, an oily substance formed in the lower layer It was extracted with benzene, and dried over 30 anhydrous magnesium sulfate The benzene was distilled off under reduced pressure to give a colorless oily substance Purification by silica gel column chromatography afforded pure N-methyl-N-(a-methylbenzyl)benzenesulfonamide in yield of 98 % This compound is designated as compound No 82 in Table 2, and its refractive index and elemental analysis values are also shown in Table 2 35 Compounds Nos 64 to 72, 74 to 77, 79 to 81, 83 to 88, and 95 to 102 shown in Table 2 could be produced in the same way as in Example 5.
EXAMPLE 6
N-Allyl-N-( 2,4-dichlorobenzoyl)-4-toluenesulfonamide 40 4.6 g ( 0 02 mole) of N-allyl-2,4-dichlorobenzamide was added to 1 2 g ( 0 024 mole) of % sodium hydride in 20 ml of dry tetrahydrofuran The mixture was stirred at room temperature for 30 minutes to react them Then, 4 2 g ( 0 024 mole) of ptoluenesulfonyl chloride was added, and reacted at room temperature for 1 hour The tetrahydrofuran was distilled off under reduced pressure After adding cold water to the residual oil, it was 45 extracted with benzene, dried over anhydrous magnesium sulfate, and concentrated to afford an oily substance It was purified by silica gel chromatography to afford compoundNo 42 shown in Table 2 in a yield of 68 % Its refractive index and elemental analysis values are also shown in Table 2.
Compounds Nos 16 to 41 and 43 to 63 in Table 2 could be prepared in the same way as in 50 Example 6.
TABLE 2
Structural formula CH 3 CR 16 so>S| -c O a) CY 17 c H 3 D s Oa N _CO.
CH 3 cl 18 O P-C C 19 CO-e Jr CH 3 _O Melting point or refractive index 1.5878 82-83 5 C 1.5912 53-54 C 48-50 C.
Elemental analysis values (%) the upper row: calculated Cthe lower row: found J C H N 54.48 3 90 54.34 3 77 53.02 4 15 4.52 4.50 4.12 53.19 4 28 4 15 48.85 3 22 4 07 48.96 3 41 47.47 3 41 4.05 3.95 47.40 3 35 3 98 62.26 5 23 62.35 5 36 4.84 X X=Ce 10.35 11 45 10.53 11 37 X=Ce 9.44 10 43 9.30 10 38 x=Ce 9.32 20 60 9.44 20 57 X=Br 9.05 22 56 9.19 22 51 11.08 4.80 11 19 S Compound No.
L^ ” 4 -1 gj C O TABLE 2 (continued) Elemental analysis values (%) Melting (the upper row: calculated) Com point or (the lower row: found / pound refractive No Structural formula index C H N S X 0 C 3OCH 3CR x=ce 21 s C / 48 14 3 50 3 74 8 57 18 95 21 < 50 om-CO 2 21 50 nz 5 1 5791 48.03 3 38 3 75 8 66 18 90 x=ce CHS co 55 64 4 36 4 33 9 90 10 95 22 -soa N-co 22 < 5 n-4 1 5750 55.51 4 40 4 35 9 78 10 87 X=Ce CH 04 CH C r 2551 62 4 06 3 76 8 61 19 05 23 O So N-COco CP o 1 5768 51.53 4 18 3 74 8 53 18 95 x=ce XC 2 2 C 4 C 56 88 4 77 4 15 9 49 10 50 24 < So?-co < n 4 1.5650 56.92 4 73 4 08 9 31 10 47 x=ce i-C 3 H 7 C_ 56 88 4 77 4 15 9 49 10 50 < SON'-CO 99-100 C. 56.75 4 70 4 18 9 53 10 43 TABLE 2 (continued) Compound No Structural formula i-C 37 CR_. 26 l Ssoa-CO C 2 27 < a /a \ a N CH Ci:C He CR 28 S a/ -'oc Q N-Bo'-co(-c 29 /a \Hc CH a CH C Ha F 3 S 1 -C / \ Melting point or refractive index D 1 5598 65.5-66 O C. 78.5-79 0 C. 39.0-40 00 C. 51.5-52 5 C. Elemental analysis values (%) {the upper row: calculated) (the lower row: found / C H N 49.24 3 62 3 59 49.38 3 76 3 52 57.22 4 20 56.98 431 4.17 4.13 51.90 3 54 3 78 51.83 3 46 3 91 60.17 4 42 59.98 4 37 44.97 3 30 45.31 3 17 4.39 10 04 4.43 9 90 3.28 3.35 S X 8.22 8.30 9.55 x=ce 10.56 9.32 10 47 8.66 X=C 1 19.15 8.70 19 03 X=F 5.95 5.90 X=I 7.50 29 71 7.63 29 65 I-. LA ti TABLE 2 (continued) Structural formula Melting point or refractive index Elemental analysis values (%) (the upper row: calculate ct (the lower row: found/ c H N S C"H CR=CH 2 CP 31 //\\S/ \,0 C 32 Q 50 p N-CO / \, 33 j-SO N-GO / \ 34 ?i CHCH?C"'6 34 \SOPN-CO /\ 49.0-49 50 C. 111 0-112,00 C. 96.0-98 00 C. 54.5-55 00 C. 57.22 4 20 56.96 4 27 51.90 3 54 52.04 3 65 4.17 4.21 3.78 3.83 47.48 2 99 3 46 47.57 3 08 64.74 5 43 65.20 5 31 3.52 4.44 4.52 9.55 10 56 9.42 10 39 x=ce 8.66 19 15 8.54 19 03 x=Cie 7.92 26 28 7.74 26 15 10.17 10.29 cjkci 4 oct aCM 3 / \ i 57.0-57 50 C. 64.74 5 43 64.80 5 33 Compound No. X 4.44 4.49 10.17 10.26 WW Compound No Structural formula %HCH-CH? OCH 2, 36/ 37 I 4 O OH 38/\ CA CHPC$ 45 C re 39 C -0 o 7 N-CO CR 1 C Ha CH=C c Q S 9-o N-CO 2 TABL Melting point or refractive index 86.0-87 O O C. 56.0-56 50 C. 26 % 1 5775 n 1 5700 n 1 5735 E 2 (continued) Elemental analysis values _(%) ( the upper row: calcul ated kthe lower row: found/ 61.61 61.45 61.61 61.50 51.01 50.90 58.36 58.02 58.36 58.24 5.17 5.24 5.17 5.23 3.78 3.85 4.61 4.81 4.61 4.75 4.23 4.35 4.23 4.15 3.50 3.42 4.00 3.97 4.00 3.95 S 9.68 9.52 9.68 9.75 8.01 8.06 9.17 9.09 9.17 9.10 X x=ce 17.72 17.65 x=ce 10.14 10.10 Xce 10.14 10.07 -J TABLE 2 (continued) Melting point or refractive Compound No Structural formula CR ik Ciclicx I C 1 41 C S>N O ” 42 c H Or 4 9 inde 43 ca HGS __ s O 1 o CL G”e(= ? S a 4-CO Elemental analysis values (%) (the upper row: calculated) (the lower row: found / X 1.5805 1.5649 1.5796 1.5953 81.0-82 O O C.
c 53.13 53.01 53.13 53.20 54.28 54.34 47.48 47.45 51.90 51.75 H 3.93 3.85 3.93 3.85 4.30 4.41 2.99 3.05 3.54 3.65 N 3.65 3.58 3.65 3.50 3.52 3.45 3.46 3.58 3.78 3.71 (A 1 P 1 t S 8.34 8.55 8.34 8.46 8.05 8.12 7.92 7.80 8.66 8.68 X x=ce 18.45 18.53 x=cie 18.45 18.50 17.80 17.72 x=ce 26.28 26.35 x=ce 19.15 19.30 TABLE 2 (continued) Compound No Structural formula CO fj H Pc H Zc WCO.
46 Ki 2 -so co / “‘ CQ 47 g // \a N-CO / k Melting point or refractive index 69.5-70 00 C.
i 8 % 1 5712 Elemental analysis values() Cthe upper row: calculated’ (the lower row: found/ c 47.48 2 99 3 46 47.62 3 03 54.31 3 70 54.34 3 63 S 7.92 3.30 7 85 X x=ce 26.28 26.36 3.96 9 06 10 02 4.05 9.22 9.91 48 Br // 5 a N-CO / 57.0-59 50 C.
c Hi 25 J 4 =Cji;a r 43.0-45 00 C.
ca S? C 2 81.0-82 O O C.
46.34 3 16 3 38 46.52 3 24 3 26 55.81 4 41 55.68 4 60 44.20 3 55 3.83 3.22 44.14 3 29 3 28 7.64 8.77 x=ce 9.69 9.65 7.38 24 47 7.53 24 61 3.75 8 90 1 0 \ H N TABLE 2 (continued) Elemental analysis values (%) Melting (the upper row: calculated) Com point or ( the lower row: found pound refractive No Structural formula index C H N S X X=Ct’ x=ce C H c 2458 03 5 16 3 98 9 11 10 08 51 502 ó 4–co t 1 5575 58.18 5 34 3 95 9 04 10 13 x=c 1,, X=CC C 2 58 03 5 16 3 98 9 11 10 08 52 ( S Oa NCO < 52 1 5671 CH 5 69 30 7 02 4 15 9 75 C a CYA 3 c 27 68 54 6 71 4 44 10 17 À 3 27 97, z N 1 5647 68.39 6 65 4 50 10 30 CHCN:CH 69 26 7 04 4 25 9 73 C 9 8 C a o H 5 C 2 CC i H 31 5630 69.35 7 11 4 20 9 65 C He-CH C Ha 3 265 23 6 39 4 23 9 68 99 C Co c N 1 5700 O 1.5700,J t 65.15 646 4 19 9./0 TABLE 2 (continued) Structural formula Melting point or refractive index Elemental analysis values (%) he upper row: calculated (the lower row: found / C H N C Ha CK=CH CH 3 C Qe-w-so 6 z c (CH( 2 r C=h 2 CR-, 101 < 502 CH j 3 CM 3 102 c NaS o c c 27 D 1 5748 1.5891 n 7 15621 1.5621 60.79 5 40 60.65 5 32 68.20 5 72 68.12 5 75 68.54 6 71 68.39 6 75 4.17 4.25 4.68 4.61 4.44 x=ce 9.55 10 56 9.63 10 65 10.71 10.82 10.17 4.40 10 29 The compounds of formula (I) provided by this invention have superior herbicidal activities, and are useful as active ingredients of herbicides for controlling various weeds in agricultural crops Examples of weeds which can be controlled by the compounds of formula (I) of this invention are various species of barnyard grass (such as Echinochloa crus-galli Beauv, Echinochloa crusgalli var oryzicola Ohwi, and Echinochloa crus-galli Subsp genuina var, echinata Honda), spikerush (Eleocharis pellucida Presl) , sedge sp. (Cyperus hakonensis saiat), umbrella plant (Cyperus difformis L), pipewort (Eriocaulon sieboldtianum Sieb), waterwort (Elatine triandra), redstem sp (Rotala indica Koehne), bulrush (Scirpus juncoides Roxb), redstem sp (Ammannia multiflorn Roxb), false pimpernel (Lindernia pyxidaria L), and slender spikerush (Eleocharis acicularis Roem et Schalt var longiseta Svenson) These examples are not limitative, and it should be understood that the compounds of formula (I) of this invention exhibit herbicidal effects also against other kinds of weeds. Compound No. S X ( Jr 1 574 477 It has been found that the compounds of formula (I) of this invention exhibit marked effects in controlling weeds which occur in fields containing much water, such as a paddy field, rather than those which occur in dry upland fields. Thus, the compounds of formula (I) exhibit excellent control effects against various species of barnyard grass, especially Echinochloa crus-gallie Beauv which is a very 5 hazardous weed in an aquatic paddy and is considered as one of the five greatest weeds in the world This weed grows in paddy fields, especially submerged paddy fields, throughout the world The compounds of formula (I) have the ability to inhibit the germination of the barnyard grass strongly and to prevent its growth in paddy fields. Moreover, the compounds of formula (I) are very characteristic in that they have 10 excellent selective herbicidal activity which ensures substantial freedom from phytotoxicity to useful agricultrual crops such as rice. Many herbicides have heretofore been suggested for application to paddy fields, and some have come into actual use Almost none of them, however, have selectivity in physiological herbicidal action between barnyard grass and rice plant The conventional 15 methods for weed killing in paddy fields are directed to the treatment of paddy fields in the rice growing stage (including the transplanting stage) to control the sprouting of barnyard grass They are based either on the utilization of the differences in resistance to herbicides between barnyard grass and rice plant according to the differences in their growing stages, or on the principle of chemical adsorption in the upper layer of soil ("artificial selectivity") 20 whereby rice plants are transplanted in such a manner that their roots are located below the herbicide-treated layer, and barnyard grass in the upper layer is controlled while protecting the rice plants from the herbicide. Barnyard grass is a graminaceous weed as rice, and they physiologically resemble each other very well Hence, controlling of barnyard grass with herbicidal chemicals often causes 25 phytotoxicity to rice plant, and it is extremely difficult to control this weed selectively in paddy fields Barnyard grass has therefore been considered to be difficult to eradicate in paddy fields, and there has been a strong demand for the advent of herbicides which can selectively control barnyard grass. The compounds of formula (I) of this invention meet this demand of agriculture They 30 have the excellent property of acting selectively on the seeds and seedlings of barnyard grass to strongly inhibit their germination, but causing no substantial phytotoxicity to rice plant This property renders the compounds of formula (I) very suitable as active ingredients of herbicides for application to paddy fields. The superior herbicidal activity of the compounds (I) of this invention can be 35 demonstrated by the experimental fact that when N-allyl-N-( 2chlorobenzoyl)benzenesulfonamide was applied at a rate of 62 5 g per 10 ares to a paddy field where rice plant and barnyard grass were simultaneously sown, the germination of the barnyard grass was completely inhibited, whereas the rice plant showed normal emergence and growth without any phytotoxicity, and that even when the rate of the compound applied was increased to 40 1.000 g per 10 ares, the rice plant showed normal germination and growth without any phytotoxicity Thus, the compound of this invention, when applied in an amount about 20 times as large as the amount required for completely controlling barnyard grass, does not exert any substantial effect on the germination and growth of rice plant. Such a high selectivity of the compounds of this invention between barnyard grass and 45 rice plant is ascribable presumably to the specific physiological activities of the compounds of this invention against barnyard grass and rice plant This superior selectivity cannot be expected from the conventional harbicides available for application to paddy fields. The compound of formula (I) of this invention may be applied directly as a herbicide. Generally, however, it is formulated into a herbicidal composition by mixing it with inert 50 liquid or solid carriers or diluents which are commonly employed in herbicide formulations. In the present invention, any inert liquid or solid carriers or diluents known in the art can be used Examples of the inert solid carrier or diluent are kaolin, diatomaceous earth, talc, bentonite, silica, and clay minerals Examples of the inert liquid carrier or diluent are water, xylene, toluene, benzene NN-dimethyl formamide, dimethyl sulfoxide, and 55 liquefied gases such as tetrafluoroethane. In addition to the inert liquid or solid carrier or diluent, the herbicidal composition may, as needed, contain surface-active agents such as polyoxyethylene monolaurate or polyethylene sorbitol in usual amounts chosen according to the form of the herbicidal composition 60 The herbicidal composition may contain the active compound of formula (I) in an amount of at least 0 5 % by weight, preferably 1 to 90 % by weight, more preferably 2 to % by weight based on the weight of the composition itself. The herbicidal composition can be in any conventional forms such as a dust, granule, wettable powder solution, emulsifiable concentrate or spray according to the method of 65 _ 28 application Any methods of formulation known in the art can be used for this purpose For example, when making a dust, granule or wettable powder, at least one active compound of formula (I) is mixed with at least one inert solid carrier or diluent The mixture is pulverized and mixed uniformly with a suitable amount of a surface active agent The solution or emulsifiable concentrate can be prepared by dissolving or dispersing at least one active 5 compound of formula (I) in at least one inert liquid carrier or diluent, followed, if desired, by adding a surface active agent. Conveniently, the amount of the active compound of formula (I) is 3 to 20 % by weight for the dust and granule, 25 to 75 % by weight for the wettable powder, and 20 to 50 % by weight for the solution and emulsifiable concentrate, all based on the weight of the resulting 10 composition. The herbicidal composition may further contain agricultural chemicals commonly used in cultivating agricultural crops, such as fungicides, insecticides, nematocides, and fertilizers. Typical examples of the funigicdes are Benomyl lmethyl 1-(nbutylaminocarbonyl)-l Hbenzimidazol-2-yl-carbamatel, Hymexazol ( 5-methyl-3-isoxazolol), Captan l 3 a,4,7,7 a 15 tetrahydro-N-(trichloromethanesulphenyl) phthalimidel, and Zineb lzinc ethylenebis(dithiocarbamate)l Examples of the insecticides are Disulfoton ( 0,0diethyl S-2ethylthioethyl phosphorodithioate) and Propoxur ( 2-isopropoxyphenyl methylcarbamate). Examples of the nematocides are MethomyllS-methyl N-(methylcarbamoyloxy) thioacetamidatel and Alidlicarb lL 2-mettlyl-2-(methylthlo) propionaldehyde 0methylcarbamoyl 20 oximel. It is also possible to incorporate at least one other herbicidally active compound used heretofore in the art into the herbicidal composition of this invention This frequently brings about a high herbicidal effect against a broad spectrum of weeds Examples of the other herbicidally active compounds include MCP ( 2-methyl-4chlorophenoxy acetic acid), 25 TOK ( 2,4-dichlorophenyl-4 '-nitrophenyl ether), Benthiocarb ( 4chlorobenzyl-N,Ndiethylthiocarbamate), Molinate (S-ethyl-N,N-hexamethylene thiocarbamate), Oxadiazonl 2-tert-butyl-4-( 2,4-dichloro-5-isopropoxyphenyl-5-oxo-1,3,4oxadiazolinel, and Butachlor l 2-chloro-2 ',6 '-diethyl-N-(butoxymethyl)acetanilidel It should be understood that these examples are not limitative and other active compounds can be equally 30 incorporated in the herbicidal composition of this invention as needed. The herbicidal compositions of this invention containing these other herbicidally active compounds are especially useful for application to paddy fields in the rice growing stage, for example to a paddy field in which transplantation has ended. The herbicide containing the compound of formula (I) as an active ingredient can be used 35 to control various weeds in areas where agricultural crops are cultivated In particular, the herbicide of this invention is effective against weeds in wet paddies rather than dry fields, and exhibits a very strong selective herbicidal effect against barnyard grass which accompanies rice plant in paddy fields, such as Echinochloa crus-galli Beauv. Herbicides containing as active ingredients 2,4,6-trichlorophenyl-4nitrophenyl ether 40 (CNP), S-( 4-chlorobenzyl)-N,N-diethylthiocarbamate (Benthiocarb), 2chloro-2 ',6 'diethyl-N-(butoxymethyl)acetanilide (Butachlor), and S-ethyl-N,Nhexamethyl enethiolcarbamate (Molinate), which now gain widespread acceptance for application to paddy fields, do not show selectivity between barnyard grass and rice plant in the germinating stage, nor are they absolutely safe to transplanted rice plants in the early stage of growth, 45 With these conventional herbicides, the risk of phytotoxicity cannot be avoided in the event of changes in the environmental condition of paddy fields, for example when rice plants are transplanted shallow at the soil surface, the soil is sandy, the water leaks, root growth is abnormal, or the temperature becomes unusually high. Since the herbicide provided by this invention is based on physiological selectivity, it has 50 the advantage of being applicable to all growing stages of rice plants ranging from the germinating to the growing stage, and being substantially free from phytotoxicity to rice plants by changes in environmental conditions Thus, its contributes greatly to the cultivation of agricultural crops. Heretofore, 3 ',4 '-dichloropropionanilide (Propanil) has been used worldwise as an agent 55 having selective activity against barnyard grass in a paddy field Propanil, however, is an agent suited for foliar application and has no effect of inhibiting germination In contrast, the herbicide of this invention exhibits far higher selective activity during the emergency of barnyard grass and rice plant than Propanil, and it is no exaggeration to say that the herbicide of this invention is an epoch-making weed killer having no equal among known 60 herbicides of this kind. As a result of fundamental and applied tests on the herbicides of this invention, it has been found that most effective, and most preferred, herbicides of this invention are those containing N-allyl-N-( 2-chlorobenzoyl) benzenesulfonamide, N-allyl-N-( 2, 4-dichlorobenzoyl)benzenesulfonamide N-propargyl-N-( 2-chlorobenzoyl) benzenesulfonamide, N 65 1 574 477 1 574 477 allyl-N-(a,a-dimethylbenzyl)benzenesulfonamide, and N-allyl-N-(amethylbenzyl)benzene sulfonamide as active ingredients These active compounds commonly have the property of strongly inhibiting the germination of barnyard grass without affecting rice plants in emergence There is, however, a slight difference in activity among these compounds For example, herbicides containing benzoyl-type active compounds have long persistence in soil 5 and can inhibit the growth of weeds for long periods of time Herbicides containing benzyl-type active compounds, on the other hand, have a very wide range of selectivity between barnyard grass and rice plant immediately after emergence. In use, the herbicide of this invention containing the active ingredient of formula (I) is applied to the locus to be protected from weeds 10 Thus, according to still another aspect of this invention, there is provided a method for controlling weeds in agricultural crops which comprises applying the compound of general formula (I) described hereinbefore to the locus to be protected from the weeds. The time of application of the compound of formula (I) is not strictly limited, and differs according to the agricultural crops and/or the weeds to be controlled Generally, in order 15 for the active compound of this invention to exhibit the best herbicidal effect, it is most convenient to apply it just before the weeds to be controlled sprout, or during their germinating stage It is of course possible to apply it to weeds after emergence, and this brings about some extent of control effect. There is no particular restriction on the locus to which the active compound of this 20 invention can be applied It can be applied to various types of agricultural land as is the case with conventional herbicides It can be best applied however to wet paddies, especially aquatic paddies in the submerged state, and when applied to upland fams of low water content, the active compound of this invention tends to have a somewhat decreased herbicidal effect 25 In order for the herbicide of this invention to exhibit its herbicidal effect most, it is applied to a field in a submerged condition before or during the germination of weeds. The active compound of formula (I) of this invention exhibits herbicidal effects against the various weeds described hereinabove, but have excellent effects of inhibiting germination of various kinds of barnyard grass, especially Echinochloa crus-galli Beauv 30 which accompany rice plants, without any substantial toxicity to rice plant Thus, the active compounds of formula (I) can be effectively applied to control barnyard grass selectively and protect rice plants therefrom. The rate of application of the active compound of formula (i) is not critical, and can be varied widely according to the type of the active compound, the time of application, the 35 procedure of application, etc It is advantageous that the rate of application of the active compound of formula (I) is generally at least 25 g, preferably 50 to 1000 g, more preferably to 500 g, per 10 ares. The method of application may be any conventional method For example, the herbicidal composition of this invention may be sprayed onto the locus to be protected from weeds 40 from above the ground or from the air Or it may be sprayed together with the seeds of an agricultural crop at the time of seeding the crop. Furthermore, according to the present invention, seeds of a crop may be dipped prior to sowing in an aqueous liquid containing the active compound of this invention to control the germination of weed seeds that may be present mixed 45 The active compounds of formula (I) of this invention have little toxicity on useful agricultural crops and low mammalian toxicity, and therefore are very suitable as herbicides. The following Examples further illustrate the formulation of the herbicides provided by the present invention, and their selective herbicidal activities 50 In these Examples, all parts and percentages are by weight The numbers of the compounds refer to those given in Table 2. Example A (wettable powder) 40 Parts of compound No 27, 55 parts of a 2:1 mixture of Zeeklite and Kunilite (a 55 trade-mark of a product of Kunimine Kabushiki Kaisha), and Sorpol 800 as a surfactant (a trademark for a product of Toho Kagaku Kogyo K K) were mixed and pulverized to form a 40 % wettable powder. Example B (emulsifiable concentrate) 60 Parts of compound No 85, 65 parts of benzene and 10 parts of Sorpol 800 as a surfactant were mixed and dissolved to form a 25 % emulsifiable concentrate. Example C (granule) Five parts of compound No 67, 50 parts of bentonite, 40 parts of Kunilite and 5 parts of 65 -30 31 1 574 477 '31 Sorpol 800 as a surfactant were mixed, and pulverized Then, 10 parts of water was added, and the mixture was uniformly stirred to form a paste The paste was extruded through a hole with a diameter of 0 7 mm, dried, and then cut to a length of 1 to 2 mm to form a 5 % granule. 5 Example D Pots ( 1/5000 are) were filled with a paddy soil in the muddy state, and barnyard grass(Echinochloa crus-galli Beauv) and other broad-leaves weeds (waterwort, pipewort, unblella plant, spikerush, sedge sp, red stem, and false pimpernel), bulurusk, and slender spikerush were sown or planted At the same time, 10 germinated rice seeds (variety: 10 Nihonbare) were sown, and two rice seedlings in the 3-lead stage were planted as one stock. Two days later, a wettable power containing each of the active compounds of this invention shown in Table 3 was weighed to a predetermined amount, diluted with 10 ml of water, and applied to the irrigated water surface in each pot Then, the treated pots were allowed to stand in a greenhouse, and the control effect and phytotoxicity on rice plants 15 were examined two weeks later. The evaluation was made on a scale of 10 grades where 0 represents normal growth and represents complete withering. The results are shown in Table 3. TABLE 3 Phytotoxicity to rice Amount Control effect of the active Trans Barn BroadActive compound plant Direct yard leaved Slender compound (g/10 ares) ation sowing grass weeds Bulrush spikerush 1000 0 3 10 4 6 4 No 16 500 0 1 8 3 1 1 250 0 O 7 1 O O 0 O 1 0 O O 1000 O O 6 3 4 O No 17 500 O O 4 1 2 O 250 O O 2 O O O O O 1 O O O 1000 O 2 10 5 7 3 No 18 500 O O 7 4 5 O 250 0 O 1 0 3 O 0 0 O O O O 1000 O 0 10 6 6 3 No 19 500 O 0 8 4 4 O 250 0 O 3 3 2 O 0 O 2 0 0 O 1000 0 O 6 3 4 0 No 20 500 0 O 3 2 2 0 250 0 O 2 0 0 0 O O O O O O TABLE 3 (continued) Phytotoxicity to rice Transplantation 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Direct sowing 2 0 0 3 1 0 2 1 0 2 1 0 0 0 0 0 0 0 Barnyard grass 7 3 4 6 2 6 3 6 3 1 7 4 2 Broadleaved weeds 2 2 1 4 3 1 3 2 1 4 1 0 3 1 0 3 2 0 Control effect Slender Bulrush spikerush 6 4 1 7 3 2 6 3 0 0 0 0 3 1 0 4 2 0 4 1 0 3 1 0 3 1 0 4 1 0 2 0 0 0 0 0 Active compound Amount of the active compound (g/10 ares) 1000 500 250 1000 500 250 No 21 No 22 No 23 No 24 No 25 No 26 1000 500 250 1000 500 250 1000 500 250 1000 500 250 TABLE 3 (continued) Phytotoxicity to rice Transplantation 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 BarnDirect yard sowing grass 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 8 9 9 Broadleaved weeds 8 3 0 7 4 1 2 1 0 3 1 0 2 0 6 3 0 Control effect Slender Bulrush spikerush 8 6 4 9 6 6 3 0 4 2 0 2 0 0 3 1 0 0 2 0 6 1 0 Active compound No 27 No 28 No 29 No 30 No 31 No 32 Amount of the active compound (g/10 ares) 1000 500 250 1000 500 250 1000 500 250 1000 500 250 1000 500 250 1000 500 250 (/I TABLE 3 (continued) Phytotoxicity to rice Control effect Barnyard grass 9 9 8 7 6 8 6 8 6 0 Broadleaved weeds 2 0 0 0 0 0 3 1 0 9 0 8 6 0 8 7 Slender Bulrush spikerush 8 6 6 4 3 8 8 8 4 0 2 0 0 0 0 0 2 0 0 8 6 0 0 0 0 7 4 1 L/I Active compound No 33 No 34 No 35 No 36 No 37 No 38 Amount of the active compound (g/10 ares) 1000 500 250 1000 500 250 1000 500 250 1000 500 250 1000 500 250 1000 500 250 Transplantation 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Direct sowing 0 0 0 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 ON TABLE 3 (continued) Phytotoxicity to rice Transplantation 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Direct sowing 3 1 4 1 0 2 0 0 0 0 0 0 0 0 0 0 0 Barnyard grass 9 8 9 9 8 4 8 6 2 9 Broadleaved weeds 6 4 0 0 0 0 3 1 0 6 4 0 0 0 0 4 0 0 Control effect Slender Bulrush spikerush 4 0 6 4 2 6 1 9 6 2 4 1 0 8, 4 0 0 0 0 0 0 3 1 0 3 0 0 0 0 0 0 0 0 0 0 Active compound No 39 No 40 No 41 No 42 No 43 No 44 Amount of the active compound (g/10 ares) 1000 500 250 1000 500 250 1000 500 250 1000 500 250 1000 500 250 1000 500 250 O Ni -I. TABLE 3 (continued) Phytotoxicity to rice Transplantation 0 0 0 0 0 0 0 0 0 q 0 0 0 0 0 0 0 0 Direct sowing 3 0 0 0 0 0 6 4 2 0 0 0 0 0 0 0 0 0 0 0 Barnyard grass 8 9 7 6 9 9 Broadleaved weeds 2 0 6 6 4 4 0 0 0 0 0 8 8 0 0 ' 8 7 4 Control effect Slender Bulrush spikerush 6 4 3 2 7 4 1 1 7 4 2 9 8 4 2 0 3 0 0 0 0 0 3 1 0 8 4 0 0 0 0 0 4 1 Active compound Amount of the active compound (g/10 ares) 1000 500 250 No 45 No 46 No 47 No 48 No 49 No 50 1000 500 250 1000 500 250 1000 500 250 1000 500 250 1000 500 250 TABLE 3 (continued) Phytotoxicity to rice BarnDirect yard sowing grass 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 9 4 2 9 3 6 3 9 6 3 8 2 0 7 3 1 Broadleaved weeds 6 4 2 4 1 0 3 1 0 2 1 0 4 1 0 2 1 0 Control effect Slender Bulrush spikerush 3 6 1 0 0 O 0 O 2 1 0 3 0 0 4 2 0 1 0 0 4 0 0 0 0 0 3 0 0 0 0 0 2 0 0 0 0 0 Active compound No 51 No 52 No 53 No 54 No 55 No 56 Amount of the active compound (g/10 ares) 1000 500 250 1000 500 250 1000 500 250 1000 500 250 1000 500 250 1000 500 250 Transplantation 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 oo ( i 10 (A j P. -P TABLE 3 (continued) Phytotoxicity to rice Amount of the active compound (g/10 ares) Control effect Transplantation 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Barnyard grass Broadleaved weeds 3 2 0 0 0 0 0 0 0 2 0 0 0 0 0 1 0 0 Active compound Direct sowing Slender Bulrush spikerush 3 1 0 0 0 0 0 0 0 0 0 0 0 0 0 4 0 0 1000 500 250 1000 500 250 1000 500 250 1000 500 250 1000 500 250 1000 500 250 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 6 2 1 0 6 4 2 7 3 4 2 0 2 0 3 0 0 0 0 0 0 0 0 0 0 1 0 0 1 0 0 4 1 0 No 57 No 58 No 59 No 60 No 61 No 62 TABLE 3 (cont) Phytotoxicity tc rice Transplant Direct ation sowing 0 0 0 0 0 0 0 0 0 0 6 2 0 7 2 0 3 1 0 0 0 0 0 0 0 0 Control effect Barnyard grass 1 0 0 0 1 0 0 9 Broadleaved weeds 6 0 0 0 0 0 0 0 7 4 9 4 Slender Bulrush spikerush 8 1 0 0 0 1 0 0 4 1 4 1 0 7 3 1 0 0 0 0 0 0 0 6 6 1 0 ()Known compound Known compound Known compound A: N-methyl-N-benzyl-2-nitrobenzene-sulfonamide B: N-2-bromoethyl-N-benzoyl-4-methylbenzene-sulfonamide Amount of the active compound (g/10 ares) 1000 500 250 1000 500 500 250 Active compound No 63 Known compound A () Known compound B () Benthiocarb (control) CNP (control) Untreated 1000 500 250 500 250 62.5 500 250 62.5 . 41 1 574 477 41 Example E Two sheets of filter paper were spread in a Petri dish with a diameter of 9 cm, and 6 ml of a wettable powder of each of the active compounds of this invention shown in Table 4 in a predetermined concentration was dropped onto them Ten seeds each of barnyard grass and rice plant (variety: Nihonbare) were directly sown The Petri dish was put into a 5 thermostat chamber at 26 C, and 72 hours later, the lengths of young stems and leaves and young roots were measured. The evaluation was made on a scale of 10 grades in which 10 represents complete inhibition and 0 represents normal growth. 10 TABLE 4 Barnyard grass Rice plant Active Concent 15 compound ration Young Root Young Root No (ppm) stem stem 1,000 7 9 0 0 300 5 7 0 0 20 64 100 4 7 0 0 2 3 0 0 1 2 0 0 1,000 10 9 0 0 25 300 7 8 0 0 100 4 5 0 0 3 5 0 0 1 2 0 0 30 1,000 9 10 0 0 300 9 9 0 0 66 100 7 5 0 0 2 3 0 0 10 1 1 0 0 35 1,000 10 10 3 2 300 10 10 1 0 67 100 10 10 0 0 30 8 7 0 0 40 5 4 0 0 1,000 10 10 0 0 300 9 10 0 0 68 100 5 8 0 0 45 3 6 0 0 2 3 0 0 1,000 7 10 0 0 300 5 7 0 0 50 69 100 3 6 0 0 1 3 0 0 0 1 0 0 1 574 477 TABLE 4 (continued) Barnyard grass Rice plant Active Concentcompound ration Young Root Young Root 5 No (ppm) stem stem 1,000 10 10 3 1 300 8 10 0 0 70 100 5 7 0 0 10 2 2 0 0 1 2 0 0 1,000 7 6 0 0 300 6 6 0 0 15 71 100 3 5 0 0 1 2 0 0 0 0 0 0 1,000 6 8 0 0 20 300 4 3 0 0 72 100 2 1 0 0 0 0 0 0 0 0 0 0 25 1,000 8 10 0 0 300 6 9 0 0 73 100 4 5 0 0 1 3 0 0 10 0 0 0 0 30 1,000 10 10 4 1 300 9 10 2 0 74 100 7 9 0 0 30 3 4 0 0 35 1 2 0 0 1,000 10 10 5 4 300 10 10 2 1 75 100 10 10 0 0 40 9 10 0 0 9 7 0 0 1 574 477 TABLE 4 (continued) Barnyard grass Rice plant Active Concentcompound ration Young Root Young Root 5 No (ppm) stem stem 1,000 10 10 7 6 300 10 10 3 2 76 100 10 10 0 0 10 9 9 0 0 9 9 0 0 1,000 10 10 5 2 300 10 10 4 1 15 77 100 10 10 1 0 9 9 0 0 8 7 0 0 1,000 10 10 7 3 20 300 10 10 4 1 78 100 8 9 0 0 7 6 0 0 6 3 0 0 25 1,000 10 10 7 6 300 10 10 5 3 79 100 9 8 1 0 7 5 0 0 10 3 3 0 0 30 1,000 10 10 6 3 300 10 9 4 2 100 10 6 0 0 30 7 2 0 0 35 2 1 0 0 1,000 10 10 8 5 300 10 10 2 2 81 100 10 6 0 O 6 2 0 O 3 1 0 O 44 1 574 477 44 TABLE 4 (continued) Barnyard grass Rice plant Active Concentcompound ration Young Root Young Root 5 No (ppm) stem stem 1,000 8 10 0 0 300 4 7 0 0 82 100 2 6 0 0 10 1 3 0 0 0 1 0 0 1,000 8 10 1 0 300 7 9 0 0 15 83 100 5 3 0 0 4 0 0 0 0 0 0 0 1,000 8 10 0 0 20 300 7 9 0 0 84 100 6 4 0 0 3 1 0 0 1 0 0 0 25 1,000 10 10 6 7 300 10 10 0 0 100 10 10 0 0 9 10 0 0 10 9 9 0 0 30 1,000 10 10 7 4 300 10 3 0 0 86 100 8 0 0 0 30 6 0 0 0 35 1 0 0 0 1,000 5 10 8 9 300 9 7 0 1 87 100 8 3 0 0 40 4 2 0 0 1 1 0 0 1 574 477 TABLE 4 (continued) Barnyard grass Active compound No. Young stem 8 6 Root 3 2 0 2 0 0 4 0 8 3 0 10 3 0 6 0 2 0 7 9 7 6 10 1 1 0 0 O 0 O Concentration (ppm) 88 Rice plant 1,000 300 1,000 300 1,000 300 Young stem 2 0 0 8 7 0 6 6 2 8 7 1 9 0 0 Root 1 1 0 0 9 3, 1 ' 0 4 0 0 4 0 0 9 2 0 0 1,000 300 1,000 300 93 1,000 300 1 574 477 TABLE 4 (continued) Barnyard grass Active compound No. 94 Concentration (ppm) 1,000 300 Young stem 7 6 1,000 300 Root Young stem 7 4 1 10 10 10 9 6 4 2 9 6 2 0 8 1 0 0 7 5 4 2 7 1 0 4 0 0 0 O O 10 10 9 10 9 4 10 6 1 7 2 0 3 0 8 8 9 6 4 8 4 2 6 2 0 2 0 0 7 6 6 4 9 2 1 7 0 0 6 0 0 Rice plant Root 9 1 0 0 7 3 0 0 1,000 300 7 1,000 300 6 1,000 300 9 7 99 1,000 300 9 8 :46 1 574 477 TABLE 4 (continued) Barnyard grass Active compound No. Concentration (ppm) 1,000 300 100 101 1,000 300 102 Benthiocarb (control) Untreated Young stem 9 8 7 4 1 1,000 300 1,000 300 6 2 6 Root Young stem 9 8 6 4 2 0 4 1 7 1 0 4 1 0 0 2 0 0 10 9 10 4 10 1 7 0 3 Example F A paddy soil was put into pots ( 1/5000 are), and the surface soil to a depth of 1 cm and 30 seeds of barnyard grass were mixed Ten seeds of rice (variety: Nihonbare) were sown on the surface of the soil, and two seedlings of rice each in the 1-leaf stage, 2-leaf stage, and 3.5-leaf stage respectively were transplanted as one stock The pots were irrigated to a water depth of 2 cm One day later, a predetermined amount of each of the active compounds of this invention indicated in Table 5 was diluted with 10 ml of water, and dropped onto the soil surface in each pot The control effect and phytotoxicity were examined in the same manner as in Example D 20 days after the treatment The results are shown in Table 5. Rice plant Root 6 3 1 0 3 1 0 0 2 1 0 0 9 6 2 TABLE 5 Amount of the active Active compound compound (g/10 ares) No 27 1000 500 250 62.5 Control effect on barnyard grass Phytotoxicity to rice Directly 1-leaf 2-leaf 3-leaf sown stage stage stage 0 0 0 0 0 0 0 0 0 O 0 O 0 O 0 O 0 O No 28 No 67 No 85 Benthiocarb (control) 1000 500 250 62.5 1000 500 250 62.5 1000 500 250 62.5 1000 500 250 62.5 1000 500 CNP 250 (control) 125 62.5 9 Untreated 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 O 0 O 0 O 0 O 0 O 0 O O 0 O O 0 O O 0 O O 0 O O 0 0 0 0 2 8 7 0 O 0 O 0 O 0 O 0 O 9 7 6 3 1 O 0 O 0 O 9 7 4 4 1 2 0 0 O 0 O Example G A test on an enlarged scale was conducted under assumed field conditions. Paddy soil was put into a concrete pot having a length of 70 cm, a width of 70 cm and a height of 50 cm and rendered muddy Sixty seeds of barnyard grass (Echinochloa crus-galli Beauv) were sown, and the pot was irrigated to a water depth of 3 cm Further, 20 germinated seeds of rice (variety: Nihonbare) were sown on the soil Threeleaf stage rice seedlings of the same variety of rice were planted in four stocks each consisting of two seedlings One day later, a granule of each of the active compounds of this invention shown in Table 6 and Benthiocarb as a control was sprayed by hand in each of the amounts indicated in Table 6 The control effect (broad-leaved grasses were those which occurred naturally) and phytotoxicity to rice were examined two weeks after the treatment The results are shown in Table 6. 1 574 477 TABLE 6 Phytotoxicity to rice Direct sowing 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Control effect Transplantation 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Barnyard grass 8 6 8 Broad-leaved weeds 2 0 0 0 0 0 0 0 0 O; 0 0 0 0 0 0 0 0 0 0 Active compound No 27 No 28 No 31 No 32 No 33 No 67 ' Amount of the active compound (g/10 ares) 1000 500 250 1000 500 250 1000 500 250 1000 500 250 1000 500 250 1000 500 250 (A -J -J 4 P TABLE 6 (continued) Active compound No 85 Benthiocarb (control) Untreated Amount of the active compound (g/10 ares) 1000 500 250 500 250 62.5 Phytotoxicity to rice Direct sowing 0 0 0 8 Transplantation 0 0 0 3 1 0 Control effect Barnyard grass 7 9 Broad-leaved weeds 0 0 0 8 2 Example H Silt loam (a clay content of 48 5 %) and sandy soil (a clay content of 15 4 %) were each placed in pots ( 1/5000 are), and agitated until a paddy field condition was attained Thirty seeds of barnyard grass (Echinochloa crus-galli Beauv) were sown per pot Further, ten germinated seeds of rice were sown, and rice seedings in the three-leaf stage were planted in two stocks each consisting of two seedlings The soil surface was submerged to a water depth of 3 cm One day later, a wettable powder of each of hhe active compounds of this invention indicated in Table 7 was applied Two weeks after the treatment, the control effect was examined in the same way as in Example D The results are shown in Table 7. Ln TABLE 7 Sandy soil Silt loam Amount of the Directly Trans Directly Transactive Barn sown planted Barn sown planted Active compound yard rice rice yard rice rice compound (g/10 ares) grass plant plant grass plant plant 500 10 0 0 10 0 0 No 27 250 10 0 0 10 0 0 10 0 0 10 0 0 62.5 10 0 0 10 0 0 500 10 0 0 10 0 0 No 31 250 10 0 0 7 0 0 10 0 0 4 0 0 62.5 4 0 0 1 0 0 500 10 0 0 10 0 0 No 32 250 10 0 0 9 0 0 9 0 0 8 0 0 62.5 7 O O 4 O O 500 10 0 0 10 0 0 No 33 250 10 0 0 9 0 0 8 0 0 7 0 0 62.5 6 0 0 4 0 0 500 10 10 10 10 10 10 Butachlor 250 10 10 10 10 10 6 (control) 125 10 10 7 10 10 3 62.5 10 10 4 7 8 0 500 10 10 10 10 10 4 Benthio 250 10 10 8 10 10 2 carb 125 10 10 6 10 10 1 (control) 62 5 10 10 3 9 8 0 0 o o O 0 O O Untreated 0 o 52 1 574 477 52 Example I Three-leaf stage rice seedlings were machine-transplanted in a paddy field, and four days after, the paddy field was divided into areas of 2 m x 2 m by vinyl resin plates A wettable powder of each of the active compounds of this invention shown in Table 8 in a predetermined amount was diluted with 400 ml of water per area and sprayed onto the entire water surface The control effect and phytotoxicity to rice were examined three weeks later. The evaluation of the control effect was made on a scale of 10 grades The phytotoxicity to rice was evaluated on the following standards: -: Normal +: slight injury ++: minor injury +++: moderate injury The results are shown in Table 8. 0 X E.'o a 1 I I 1 1 11 1 1 1 1 + + 1-4 o t\ \o 0 Ocm O o\eon O \p\ O m 10 \ t Ct_ -) Do4 \ C) O O O =C=r ao',r-t O oo WV,)=000 O oooze ooc,->t ooo’r op S Loo mr 00 ‘C t C 00 ovr 01 fm C 8 in N 4 m 8 V) N m N 4 o _,z z Z V) z a c) ct 0) ra D mam \ono Ino4 =o a mC.
C) -C -4 U) E< c m HCa W to I-OCOO) _. 0 8 d > -u 00 > P.
< 3 r 1 574 477 53 1 574 477 53 Claims (1) WHAT WE CLAIM IS: 1 A compound of the general formula RR 4 R 5 1 R O YR RK+/R, a s 5 R 3 R 8 RB 7 wherein R O represents an alkyl group optionally having a substituent selected from a cyano 10 group, lower alkoxy groups and di(lower alkyl)amino groups, a lower alkenyl group, or a lower alkynyl group; R 1, R 2 and R 3, independently from each other, represent a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group; R 4, R 5, R 6, R 7 and R 8, independently from each other, represent a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group; Y represents a group of the formula 15 o R 9 -C or a group of the formula -C 20 R 10 in which one of R 9 and Ro is a lower alkyl group and the other is a hydrogen atom or a lower alkyl group; with the proviso that when Y is the group 25 0 II -C 30 and Ro represents an unsubstituted alkyl group, R 4, Rs, R 6, R 7 and R 8 do not represent hydrogen atoms at the same time. 2 A compound of claim 1 wherein Ro represents an alkyl group containing up to 15 carbon atoms which may contain a substituent selected from a cyano group, lower alkoxy 35 groups and di-(lower alkyl)amino groups; a lower alkenyl group; or a propargyl group. 3 A compound of claim 1 wherein R O is an allyl or propargyl group. 4 A compound of claim 1, 2 or 3 wherein Y represents the group 40 -C, and at least one of R 4, R 5, R 6, R 7 and R 8 is a halogen atom and the rest are hydrogen 45 atoms. A compound of claim 1, 2 or 3 wherein Y represents the group 50 l R 9 -C, R O O 55 and R 4, R 5, R 6, R 7 and R 8 all represent hydrogen atoms. 6 A compound of claim 1 which is a compound of the general formula R O a 41 R 160 R 2 o 1 RB 1 R-71 _Y( wherein Rol represents an alkyl group containing up to 15 carbon atoms which may contain a substituent selected from a cyano group, lower alkoxy groups and di(lower alkyl)amino groups, a lower alkenyl group, or a propargyl group; R 1, and R 21, independently from each other, represent a hydrogen atom, a halogen atom, a methyl group, an ethyl group, or a methoxy group, R 41, Rs 1, R 61, R 71 and R 81, independently from each other represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group; Y 1 represents the 5 group o R 91 11 10 -C or -CI R 101 in which one of R 91 and R 101 is a methyl or ethyl group, and the other is a hydrogen atom or 15 a methyl or ethyl group; with the proviso that when Y 1 is the group CO and R 01 is an unsubstituted alkyl group, R 41, R 51, R 61, R 71 and R 81 do not represent hydrogen atoms at the same time. 7 A compound of claim 6 wherein R 01 represents an allyl or propargyl group, and Y 1 represents the group -CO-, -CH(CH 3) or -C(CH 3)28 A compound of claim 6 wherein Rm 1 represents an allyl or propargyl group and Y 1 represents the group -CO-. 9 A compound of claim 8 wherein R 41 is a halogen atom, and one of R 51, R 61, R 71 and R 81 is a hydrogen atom or a halogen atom, and the rest are hydrogen atoms. 10 A compound of claim 8 wherein R 41 is a halogen atom, R, and R 21, independently 25 from each other, represent a hydrogen atom or a methyl group and Rs 51, R 61, R 71 and R 81, independently from each other, represent a hydrogen atom or a methyl group. 11 A compound of claim 9 wherein R 1, and R 21, independently from each other, represent a hydrogen atom or a methyl group. 12 A compound of claim 6 wherein R 1 is an allyl group and Y 1 is the group -CH(CH 3) 30 or -C(CH 3)2-. 13 A compound of claim 12 wherein R, represents a hydrogen atom, a methyl group or a methoxy group, R 21 is a hydrogen atom, R 41 and R 61, independently from each other, represent a hydrogen atom, a halogen atom, or a methyl group and R 51, R 71 and R 81 are all hydrogen atoms 35 14 A compound of claim 1 which is a compound of the formula ( SO?-N-RCO 2 (t-b' 40 wherein R 02 is an allyl or propargyl, and X 1 is a hydrogen or chlorine atom. The compound of claim 1 which is N-allyl-N-( 2-chlorobenzoyl)benzene 45 sulfonamide. 16 The compound of claim 1 which is N-allyl-N-( 2,4-dichlorobenzoyl) benzenesulfonamide. 17 The compound of claim 1 which is N-propargyl-N-( 2-chlorobenzoyl) benzenesulfonamide. 18 A compound of claim 1 which is a compound of the formula 50 CH_CH c < 95 2>-Yt (I a 12 55 wherein Y 2 is the group CH 3 CH 3 60 I 60 -CH or -C-, CH 3 CH 3 and X 2 is a hydrogen or chlorine atom.
1 574 477 1 574 477 55 19 The compound of claim 1 which is N-allyl-N-(a,a-dimethylbenzyl)benzenesulfonamide.
The compound of claim 1 which is N-allyl-N-(a-methylbenzyl) benzenesulfonamide.
21 The compound of claim 1 which is N-allyl-N-(a-methyl-4-chlorobenzyl) benzenesulfonamide 5 22 The compound of claim 1 which is N-allyl-N-(a,a-dimethyl-4chlorobenzvl)benzenesulfonamide.
23 Any of the compounds according to claim 1 that are hereinbefore described in the Examples, other than the compounds of claims 15-17 and 19-22 10 24 A process for preparing a compound according to claim 1, which comprises (a) reacting a benzenesulfonamide derivative of the general formula RI,___ RO R O-)1 M( 15 a, 5 wherein M represents a hydrogen atom or an alkali metal atom, and R 1, R 1, R 2 and R 3 are as defined in claim 1, with a compound of the general formula a Rs 20 X 3;-YvDownload PDF in English